Controlling process gases

ABSTRACT

Biomass (e.g., plant biomass, animal biomass, and municipal waste biomass) is processed to produce useful intermediates and products, such as energy, fuels, foods or materials. For example, equipment, systems and methods are described that can be used to treat feedstock materials, such as cellulosic and/or lignocellulosic materials, in a vault in which hazardous gases are removed, destroyed and/or converted. The treatments are efficient and can reduce the recalcitrance of the lignocellulosic material so that it is easier to produce an intermediate or product, e.g., sugars, alcohols, sugar alcohols and energy, from the lignocellulosic material.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/299,006, filed Jun. 9, 2014, which is a continuation application ofPCT/US14/21630 filed Mar. 7, 2014, which claims priority to thefollowing provisional applications: U.S. Ser. No. 61/774,684, filed Mar.8, 2013; U.S. Ser. No. 61/774,773, filed Mar. 8, 2013; U.S. Ser. No.61/774,731, filed Mar. 8, 2013; U.S. Ser. No. 61/774,735, filed Mar. 8,2013; U.S. Ser. No. 61/774,740, filed Mar. 8, 2013; U.S. Ser. No.61/774,744, filed Mar. 8, 2013; U.S. Ser. No. 61/774,746, filed Mar. 8,2013; U.S. Ser. No. 61/774,750, filed Mar. 8, 2013; U.S. Ser. No.61/774,752, filed Mar. 8, 2013; U.S. Ser. No. 61/774,754, filed Mar. 8,2013; U.S. Ser. No. 61/774,775, filed Mar. 8, 2013; U.S. Ser. No.61/774,780, filed Mar. 8, 2013; U.S. Ser. No. 61/774,761, filed Mar. 8,2013; U.S. Ser. No. 61/774,723, filed Mar. 8, 2013; and U.S. Ser. No.61/793,336, filed Mar. 15, 2013. The full disclosure of each of theseapplications is incorporated by reference herein.

BACKGROUND OF THE INVENTION

Many potential lignocellulosic feedstocks are available today, includingagricultural residues, woody biomass, municipal waste, oilseeds/cakesand seaweed, to name a few. At present, these materials are oftenunder-utilized, being used, for example, as animal feed, biocompostmaterials, burned in a co-generation facility or even landfilled.

Lignocellulosic biomass includes crystalline cellulose fibrils embeddedin a hemicellulose matrix, surrounded by lignin. This produces a compactmatrix that is difficult to access by enzymes and other chemical,biochemical and/or biological processes. Cellulosic biomass materials(e.g., biomass material from which the lignin has been removed) is moreaccessible to enzymes and other conversion processes, but even so,naturally-occurring cellulosic materials often have low yields (relativeto theoretical yields) when contacted with hydrolyzing enzymes.Lignocellulosic biomass is even more recalcitrant to enzyme attack.Furthermore, each type of lignocellulosic biomass has its own specificcomposition of cellulose, hemicellulose and lignin.

SUMMARY

Generally, the inventions relate to methods, equipment and systems fortreating materials, such as biomass. The inventions also relate tomethods, systems and processing equipment used for producing productsfrom a biomass material. Generally, the methods include treating arecalcitrant biomass, (e.g., with electron beams or other ionizingradiation) to reduce the recalcitrance of the biomass, optionally whileconveying the biomass using one or more conveyor(s) and optionally in anenclosure, such as a vault. Included in the methods, hazardous and/ornoxious gases which are produced can be filtered or destroyed. In someimplementations, the methods further include biochemically and/orchemically processing the reduced recalcitrance material to, forexample, ethanol, xylitol and other useful and valuable products.

Radiation in a confined space containing gases and/or organic material(e.g., air, biomass and/or hydrocarbons), can create reactive gases,e.g., ozone, oxides of nitrogen and/or Volatile Organic Compounds(VOCs), such as methane, ethane, ethylene, formic acid, acetic acid,methanol, formaldehyde, acetaldehyde and acetylene, and/or otherairborne agents e.g., Hazardous Air Pollutants (HAPs), such as soot. Inaddition, accidental release of processing gases from equipment, such asSF₆, can be a hazard. The gases can degrade processing equipment andcause equipment wear and failure, incurring costs due to downtime andnecessary repairs. The gases also should be removed (e.g., removed,sequestered, filtered, concentrated) and/or destroyed before operatorscan access the interior of the confined spaces. Finally, the gasesshould be isolated (e.g., removed, sequestered, filtered) and/ordestroyed prior to being released into the environment. Mitigation ofthese issues can be accomplished by controlling the atmosphere insidethe confined space or near the processes, for example, by flushingand/or purging a processing vault with an inert gas (e.g., nitrogen orargon), and ensuring that any process gases are removed from the vault.In addition, any hazardous gases can be filtered and/or destroyed by afiltering system.

In some instances, the invention relates to methods for processingmaterials (e.g., biomass including lignocellulosic, cellulosic orstarchy material). The method includes impinging a substantially inertgas on a foil window of an electron beam horn while passing electronsthrough the window and inert gas while processing the material. The foilcan have a surface communicating with a high vacuum side of anaccelerator tube. The foil, along with a secondary foil can define aspace about which the substantially inert gas traverses. Optionally, thepressure inside the space is greater than atmospheric pressure (e.g.,between about 50 and 200 psi). The inert gas can include nitrogen (e.g.,at least 80% nitrogen, at least 90% nitrogen, at least 95% nitrogen, atleast 99% nitrogen). Optionally the method includes recycling the inertgas, for example, the inert gas can be impinged on the foil window morethan one time before it is discarded. The inert gas can be processed ortreated, for example, prior to or before being utilized, or before usingthe gas again in the method that includes recycling the gas. Optionally,the inert case is treated after impinging electrons on the foil window.Optionally, treating the gas includes filtering the gas. For example,treating the inert gas can include removing from the inert gascontaminants or undesired components that include oxygen, ozone, oils,particulates, water and mixtures thereof. Treating can also includeremoving volatile organic compounds.

In some cases the invention relates to systems for processing materials,e.g., biomass, where the system includes a flow path for providing asubstantially inert gas through a space, wherein the space is definedby, a first foil in communication with the vacuum side of a scanninghorn of an electron beam accelerator and a secondary foil disposedfacing the first foil window. Optionally, the secondary foil can bemounted on an enclosure. The flow path can optionally include a firstconduit and inlet for flowing the inert gas into the space and a secondconduit and outlet for flowing the inert gas out of the space. The firstand second conduit are in fluid communication through the space. Thefirst conduit and/or inlet and second conduit and/or outlet can be sizedso that the pressure inside the space is above atmospheric pressure(e.g., between about 50 and 200 psi).

In another aspect of the invention, the methods include reducing therecalcitrance of biomass (e.g., biomass) while producing or generating ahazardous gas. For example hazardous gases can include gases selectedfrom the group consisting of ozone, volatile organic compounds,hazardous air pollutants, particulates, soot, nitrogen oxides andmixtures of these. The methods include flowing the hazardous gas througha filtering system. The hazardous gas can include a hazardous componentand a non-hazardous component and the filtering system is configured toremoved and/or destroy by the hazardous component. Optionally, thefilter system can include a carbon filter disposed in the flow of thehazardous gas. Optionally, the method includes conveying the biomasswhile reducing its recalcitrance.

Optionally, reducing the recalcitrance of the biomass material occurs ina vault. For example, the concentration of hazardous gas can be reducedby flowing gas that is in the vault through the filter system to theexterior of the vault and flowing gas from the exterior of the vault tothe interior of the vault. For example, a make-up gas is flowed from theexterior of the vault to the interior of the vault while the hazardousgas is flowed from the interior of the vault to the exterior of thevault and through the filtering system. The filtering system can bedisposed outside of the vault or inside the vault. Optionally, gasflowing from the exterior of the vault (e.g., a make-up gas) comprisesan inert gas. Also optionally, the method can include maintaining anegative pressure in the vault by flowing the gas that is in the vault(e.g., through the filter system) to the exterior of the vault at afaster flow rate than flowing the gas from the exterior of the vault tothe interior of the vault (e.g. the make-up gas). For example, the flowrate to the exterior of the vault is at least 2 times faster than theflow rate to the interior of the vault (e.g., at least 3 times faster,at least 4 times faster, at least 5 times faster). In some instances,the flow rate to the exterior of the vault is between about 1000 and10000 CFM and the flow rate to the interior of the vault is betweenabout 10 and 5000 CFM. Optionally, the method can include conveying thebiomass from the interior of the vault to the exterior of the vault,extracting hazardous gases from the biomass, and flowing the hazardousgases through the filter system. For example, the hazardous gases can beextracted from the biomass in the vault or the hazardous gases can beextracted from the biomass once it has been conveyed out of the vault.

Optionally, the recalcitrance of the biomass material can be reduced byexposing the biomass material to ionizing radiation. For example, theionizing radiation can be produced by an electron accelerator comprisinga scanning horn equipped with a metal foil electron extraction window,and the method can further include directing a gas (e.g., a cooling gas)against the extraction side of the foil electron extraction window.

In some aspects, the invention includes a system for processing amaterial in a vault. The vault can contain an electron irradiationdevice configured to irradiate a biomass material, e.g., while it isconveyed on a conveyor. The system can also include a process gastreating system, e.g., a system for treating gases produced during theprocessing of the biomass. Optionally the process gas treating systemincludes a gas path from the exterior of the vault to the interior ofthe vault, the gas path continuing through the vault, and then the gaspath continuing from the interior of the vault to the exterior of thevault. A filter can be placed in the gas path. For example, the filtercan be placed inside the vault in the gas path or outside of the vaultin the gas path. The filter can be placed outside the vault andconfigured to process gasses that flow through the vault (e.g., processgases). The gas path through the vault can include a gas path through awindow cooling system. For example, the window cooling system caninclude a manifold configured to accept a gas from a conduit and themanifold can be also configured for impinging the gas against a firstwindow mounted on the vacuum side of a scan horn of the irradiationdevice. The window cooling system can also include a second windowfacing the first window, wherein the first and second window define aspace and the space includes an outlet configured to allow the gas toexit the space. For example, the gas path can include a path through thespace. Optionally, the gas path through the vault includes a paththrough an intake manifold.

The equipment, systems and methods described herein are effective inmitigating process gases produced during biomass processing.

Implementations of the invention can optionally include one or more ofthe following summarized features. In some implementations, the selectedfeatures can be applied or utilized in any order while in otherimplementations a specific selected sequence is applied or utilized.Individual features can be applied or utilized more than once in anysequence and even continuously. In addition, an entire sequence, or aportion of a sequence, of applied or utilized features can be applied orutilized once repeatedly or continuously in any order. In some optionalimplementations, the features can be applied or utilized with different,or where applicable the same, set or varied, quantitative or qualitativeparameters as determined by a person skilled in the art. For example,parameters of the features such as size, individual dimensions (e.g.,length, width, height), location of, degree (e.g., to what extent suchas the degree of recalcitrance), duration, frequency of use, density,concentration, intensity and speed can be varied or set, whereapplicable as determined by a person of skill in the art.

Features, for example, include: a method of processing a material;impinging a substantially inert gas on a foil window of an electron beamhorn and passing electrons through the window and inert gas whileprocessing a material; a foil that has a surface communicating with ahigh vacuum side of an accelerator tube; a foil and a secondary foilthat defines a space about which a substantially inert gas traverses; apressure inside a space (e.g., defined by a foil and a secondary foil)that is greater than atmospheric pressure; an inert gas that comprisesnitrogen; recycling an inert gas; impinging a substantially inert gas ona foil window more than one time before discarding it; treating an inertgas; treating an inert gas by a method that includes filtering the gas;removing oxygen from an inert gas; removing ozone from an inert gas;removing oils from an inert gas; removing particulates from an inertgas; removing water from an inert gas; processing a biomass material;processing a lignocellulosic material; processing a cellulosic material;utilizing vaults constructed with low porosity bricks.

Features, for example, can also include: a system for processingbiomass; a flow path for providing a substantially inert gas through aspace, wherein the space is defined by a first foil in communicationwith the vacuum side of a scanning horn of an electron beam acceleratorand a secondary foil disposed facing the first foil; a secondary foilthat is mounted on an enclosure; a flow path that includes a firstconduit and an inlet for flowing an inert gas into a space and a secondconduit and an outlet for flowing the inert gas out of the space,wherein the first conduit and second conduit are in fluid communicationthrough the space; a first conduit and/or inlet and a second conduitand/or outlet that are sized so that the pressure inside the space isgreater than atmospheric pressure.

Features, for example, can also include: a method for processing abiomass material; producing a hazardous gas while reducing therecalcitrance of a biomass material, and flowing the hazardous gasthrough a filtering system; reducing the recalcitrance of a biomassmaterial in a vault; a filtering system disposed outside of a vault forfiltering process gases generated inside the vault; a make-up gas thatis flowed from the exterior of the vault to the interior of the vaultwhile a hazardous gas is flowed from the interior of the vault to theexterior of the vault and through a filtering system; a make-up gas fora vault that comprises an inert gas; maintaining a negative pressure ina vault by flowing a gas that is in the vault through a filtering systemto the exterior of the vault at a faster flow rate than flowing amake-up gas from the exterior of the vault to the interior of the vault;maintaining a negative pressure in a vault by flowing a gas that is inthe vault through a filtering system to the exterior of the vault at aflow rate that is at least two times faster than flowing a make-up gasfrom the exterior of the vault to the interior of the vault; maintaininga negative pressure in a vault by flowing a gas that is in the vaultthrough a filtering system to the exterior of the vault at a flow ratethat is at least three times faster than flowing a make-up gas from theexterior of the vault to the interior of the vault; maintaining anegative pressure in a vault by flowing a gas that is in the vaultthrough a filtering system to the exterior of the vault at a flow ratethat is at least four times faster than flowing a make-up gas from theexterior of the vault to the interior of the vault; maintaining anegative pressure in a vault by flowing a gas that is in the vaultthrough a filtering system to the exterior of the vault at a flow ratethat is at least five times faster than flowing a make-up gas from theexterior of the vault to the interior of the vault; maintaining anegative pressure in a vault by flowing a gas that is in the vault tothe exterior of the vault at a rate of between 1000 and 10,000 CFM andflowing a make-up gas from the exterior of the vault to the interior ofthe vault at a flow rate of between about 10 and 5000 CFM; utilizing avault constructed of low porosity materials; utilizing a vaultconstructed of low porosity concrete; utilizing a vault with wallsconstructed of low porosity bricks; conveying a biomass from theinterior of a vault to the exterior of the vault, extracting hazardousgases from the biomass, and flowing the hazardous gases through a filtersystem; reducing the recalcitrance of the biomass material by exposingthe biomass material to ionizing radiation; producing ionizing radiationby an electron accelerator comprising a scanning horn equipped with ametal foil electron extraction window, and directing a cooling gasagainst the extraction side of the foil electron extraction window; agas filtering system that includes a carbon filter disposed in the flowof a hazardous gas; a hazardous gas that includes ozone; a hazardous gasthat includes volatile organic compounds; conveying a biomass materialwhile reducing the recalcitrance of the biomass material; a hazardousgas that includes a hazardous component and a non-hazardous componentand a filtering system that is configured to remove the hazardouscomponent; a hazardous gas that includes a hazardous component and anon-hazardous component and a filtering system that is configured todestroy the hazardous component.

Features, for example, can also include: a system for processing amaterial in a vault; a vault containing an electron irradiation deviceconfigured to irradiate a biomass material, and a process gas treatingsystem comprising a gas path that includes a path from the exterior ofthe vault to the interior of the vault, through the vault, and to theexterior of the vault; a gas filter in a gas path; a gas path through avault includes a gas path through a window cooling system and the windowcooling system comprises a manifold configured to accept a gas from aconduit and impinging the gas against a first window mounted on thevacuum side of a scan horn of an irradiation device; a window coolingsystem that includes a first window mounted on the vacuum side of a scanhorn of an irradiation device and a second window facing the firstwindow, wherein the first and second window define a space and the spaceincludes an outlet configured to allow the gas to exit the space; a gaspath through a vault that includes a path through an intake manifold; afilter that is positioned outside of a vault and configured to filter agas that has flowed through the vault.

Other features and advantages of the invention will be apparent from thefollowing detailed description, and from the claims.

DESCRIPTION OF THE DRAWING

FIG. 1 shows an embodiment of the invention, including a perspectiveview of a vault with its roof and ceiling not shown and some componentsof a process gas mitigation system.

FIG. 2 is a side view of the gas mitigation system components shown inFIG. 1.

FIG. 3A is a detailed side view showing part of the gas mitigationsystem including a system for air cooling window foils. FIG. 3B is ahighly enlarged detail view of area 3B in FIG. 3A. FIG. 3C is anenlarged detailed perspective view of the electron scanning horn, windowcooling system and conveyor.

DETAILED DESCRIPTION

Using the equipment, methods and systems described herein, cellulosicand lignocellulosic feedstock materials, for example, that can besourced from biomass or processed biomass (e.g., plant biomass, animalbiomass, paper, and municipal waste biomass) and that are generallyreadily available, can be turned into useful products (e.g., sugars suchas xylose and glucose, sugar alcohols and other alcohols such as ethanoland butanol. Described herein are methods and systems for removing(e.g., filtering, destroying, diluting, converting) process gases, forexample, ozone and VOCs, produced during biomass processing, e.g.,during irradiation of the biomass with an electron beam.

Processes for manufacturing sugar solutions and products derivedtherefrom are described herein. These processes can include, forexample, optionally mechanically treating a cellulosic and/orlignocellulosic feedstock. Before and/or after this treatment, thefeedstock can be treated with another treatment, for example,irradiation, steam explosion, pyrolysis, sonication, chemical treatment(e.g., acid, base or solvents) and/or oxidation to reduce, or furtherreduce its recalcitrance. A sugar solution is formed by saccharifyingthe feedstock by, for example, the addition of one or more enzymesand/or one of more acids. A product can be derived from the sugarsolution, for example, by fermentation to an alcohol or hydrogenation toa sugar alcohol. Further processing can include purifying the solution,for example, by distillation. If desired, the steps of measuring lignincontent and setting or adjusting process parameters (e.g., irradiationdosage) based on this measurement can be performed at various stages ofthe process, for example, as described in U.S. Pat. No. 8,415,122 issuedApr. 9, 2013, the complete disclosure of which is incorporated herein byreference.

Since the recalcitrance reducing treatment step can be a high energyprocess, the treatment can be performed within an enclosure, e.g., avault and/or bunker system to contain the energy and/or some of theproducts, e.g., process gases, derived from the energetic process, whichcould otherwise be hazardous. For example, the vault can be configuredto contain heat energy, electrical energy (e.g., high voltages, electricdischarges), radiation energy (e.g., X-rays, accelerated particles,gamma-rays, ultraviolet radiation), explosion energy (e.g., a shockwave, projectiles, blast wind), gases (e.g., ozone, steam, nitrogenoxides and/or volatile organic compounds) and combinations of these.Although this containment protects people and equipment outside of thevault, the equipment inside the vault is subjected to the energy and/orproducts derived from the energetic process. In some cases, thiscontainment can exacerbate the negative effects, for example, by notallowing dissipation of gases and particulates (e.g., fines, dust, soot,carbon containing fine particles, ozone, steam, nitrogen oxides and/orvolatile organic compounds). For example, many electron beam systemshave delicate window structures that can be damaged by process gases orparticulates. The deleterious effects of hazardous gases andparticulates can be mitigated by diluting, removing converting and/ordestroying any process gases and/or particulates.

If treatment methods for reducing the recalcitrance include irradiationof a feedstock (e.g., cellulosic or lignocellulosic feedstock or evenhydrocarbon-containing feedstocks), for example, with ionizingradiation, ozone may be produced by the irradiation of oxygen (e.g.,oxygen present in air). Oxides of nitrogen can also be produced byirradiation of air, as described in “Toxic Gas Production at ElectronLinear Accelerators”, W. P. Swanson, SLAC-PUB_2470, February 1980, theentire disclosure of which is incorporated herein by reference. Theirradiation can also cause heating and decomposition of the biomassmaterial that can release and/or produce VOCs, HAPs andcarbon-containing particulates (e.g., soot). Ozone is a strong oxidantwith a redox potential of 2.07 V (vs the Standard Hydrogen Electrode:SHE), higher than other known strong oxidants such as hydrogen peroxide,permanganate, chlorine gas and hypochlorite with redox potentials of1.77 V, 1.67 V, 1.36 V and 0.94 V, respectively. Therefore, materials,for example, organic materials, are susceptible to degradation byionizing radiation and oxidation by ozone. For example, the materialscan degrade through chain scission, cross-linking, oxidation andheating. In addition, metal components are susceptible to oxidation anddegradation by ozone causing them, for example, to corrode/pit and/orrust. Soot and VOCs can be hazardous and/or damaging to equipment, forexample, posing a breathing hazard and/or coating and interfering withthe operation of equipment. Soot can also damage delicate windows (e.g.,window foils) utilized for electron extraction in irradiation devices.

Therefore, equipment that includes polymers and some metals (e.g.,excluding perhaps corrosion resistant or noble metals) can be damaged.For example, damage can occur to belts that include organic material,for example, those used in equipment, e.g., as the coupling between adrive motor and an eccentric fly wheel of a vibratory conveyor. Systemsand/or motor components that can be susceptible to damage by ozone andradiation include, for example, wheels, bearings, springs, shockabsorbers, solenoids, actuators, switches, gears, axles, washers,adhesives, fasteners, bolts, nuts, screws, brackets, frames, pulleys,covers, vibration dampeners, sliders, filters, vents, pistons, fans, fanblades, wires, wire sheathing, valves, drive shafts, computer chips,microprocessors, circuit boards and cables. Some organic materials thatcan be degraded by ionizing radiation and ozone include thermoplasticsand thermosets. For example, organic materials that can be susceptibleto damage include phenolics (e.g., bakelite), fluorinated hydrocarbons(e.g., Teflon), thermoplastics, polyamides, polyesters, polyurethanes,rubbers (e.g., butyl rubber, chlorinated polyethylene, poly norbornene),polyethers, polyethylene (linear low density polyethylene, high densitypolyethylene), polystyrenes, polyvinyls (e.g., poly vinyl chloride),cellulosics, amino resins (e.g., urea formaldehyde), polyamines,polyamides, acrylics (e.g., methyl methacrylate), acetals (e.g.,polyoxymethylene) lubricants (e.g., oils and gels), polysiloxanes andcombinations of these.

FIG. 1 depicts an embodiment of the invention shown as a top perspectiveview. The view shows enclosing walls 110 (in the form of blocks) of avault with doors 112 and foundation 113. In the particular embodimentshown, the walls are made of blocks, the walls having a thickness ofapproximately six feet. The ceiling/roof is not shown so the interior ofthe vault can be more clearly described. The view includes a highvoltage (e.g., 1 MV) power source 120 and an electrical conduit 122connecting the power source to the electron accelerator 124. In thisembodiment, the electrical conduit 122 is a “pipe in a pipe” design withinsulating gas, e.g., SF₆, between pipes. Distal (D) end of accelerator124 has been leaded to prevent X-rays from emanating from the distal endof 124. The power source, electrical conduit and electron acceleratorare supported by the concrete roof of the vault, outside the vault. Theelectron accelerator is connected to a scan horn 128 by a conduit 130(high vacuum electron guide) that passes through the concrete ceiling(e.g., 4 to 6 feet thickness). A conveyor 132 is positioned forconveying biomass under the scan horn while the scan horn irradiates thebiomass. A window cooling air conduit 140 brings air from outside thevault through the ceiling and is connected to a system 200 for blowingthe cooling air across an electron extraction window, e.g., a titaniumfoil window. The vault also includes an air conduit 144 for removing theair and other gases, such as process gases (e.g., hazardous gases, HAPs,VOCs), from the interior of the vault to the exterior of the vault. Airconduit 144 is fed by air intake manifold 182 that can include vents(e.g., configured as a screen, grill or mesh), for example 184.Component 182 can include screens, filters and/or air flow controllers.Ideally manifold 182 does not significantly reduce the air flow. In someinstances air flow into the vault is on the order of 1000 CFM and airflow out is on the order of 5000 CFM, which maintains a negativepressure inside the vault. In this embodiment, the outer perimeter ofthe vault can be about 34×34 feet and the ceiling height can be about 8feet. The interior volume of the vault is therefore about 4600 cubicfeet. The turnover rate of the atmosphere can be at least about 0.25turnover per minute (e.g., at least about 0.5 turnovers, at least 1turnover per minute, at least about 2 turnovers per minute, at leastabout 3 turnovers per minute, at least 4 turnovers per minute, at least5 turnovers per minute, or between 1 and 5 turnovers per minute, betweenabout 2 and 4 turnovers per minute). The turnover rate is the rate ofgas exchange in the vault.

Construction materials can be chosen to increase the containment ofprocesses gases in vault and improve the lifetime of the vault (e.g., byreducing corrosion). For example, the porosity of the walls can bereduced by infusion of materials into the construction blocks. Forexample, concrete with lower permeability can generally be achieved bysubstituting between 25 to 65 percent slag cement for Portland cement.Finely-divided solids (e.g., lime, silicates and colloidal silica) addedto the cement when the blocks are made can reduce permeability to waterand gases by increasing the density or by filling up voids. Somecrystalline admixtures react with water and cement particles in theconcrete to form calcium silicate hydrates and/or pore-blockingprecipitates in the existing microcracks and capillaries. The resultingcrystalline deposits, which are analogous to calcium silicate hydrateformation, become integrally bound with the hydrated pastes. Porosityreducing additives can also include hydrophobic water-repellentchemicals based on soaps and long-chain fatty acids derivatives,vegetable oils (tallows, soya-based materials, and greases), andpetroleum (mineral oil, paraffin waxes, and bitumen emulsions). Thesematerials are more useful for providing a water repellency layer on thematerial and would be more usefully applied to the exterior portions ofthe vault to aid in decreasing interior vault humidity, which canexacerbate corrosion in the vault. In addition, to improve the life ofthe structures, the interior surfaces (e.g., of concrete blocks) can becoated or covered with a corrosion resistant material, such as stainlesssteel.

FIG. 2 is a right side view of the process gas (e.g., hazardous gas)mitigation system components some of which were introduced in FIG. 1. InFIG. 2 the vault walls, foundation, irradiator power source andelectrical conduit for the power source are omitted for clarity. Ablower system 170 blows air into the vault in the direction shown by thearrows. For example, air is shown on the left side of the drawing beingblown from the outside of the vault 171, though a ceiling inlet 172(which is often leaded), and down a conduit 140, to an air outlet insidethe vault 174 that is an outlet of a window cooling system to bedescribed in detail with reference to FIG. 3A. Therefore, an air flowpath from outside the vault to the interior is provided through system170, conduit 140, through the interior of the window cooling system(described with ref to FIGS. 3A and 3B), and outlet 174 for thisembodiment. Other gas inlets into the vault can be utilized if desired,for example, to cool a product or equipment in the vault.

Air in the vault is extracted out of the vault in the directions shownby the arrows on the right side of the drawing. In particular, air isdrawn through grills (e.g., screen, mesh) disposed on exhaust manifold182 as previously described. System 180 includes fans/blowers, and orgrills (e.g., screens, mesh) and/or air pumps for drawing air intomanifold 182, up conduit 144, and out of the vault. The air is made topass through a process case, such as an ozone destruction system, e.g.,a carbon filter that destroys any process gas, such as ozone (convertingit to oxygen) and adsorbs or destroys volatile organic compounds. Thedestruction system can be disposed anywhere in the flowing air path thatpasses through 182, 144 and 180 and before the air is vented to theatmosphere. In some embodiments, it is preferable to have destructionsystems in manifold 182 so that venting pipe 144 is not exposed toprocess gases, e.g., ozone. In other embodiments it is preferred to havedestructor systems located in system 180 and configured to be quicklyreplaced so that minimal or no down time is required for maintenance. Insome cases the destructor systems (e.g., carbon filters) can be mountedto be automatically replaced when sensors indicated the need (e.g.,ozone levels, VOCs and/or HAPs are higher than background levels). Ventson 180 (not shown), exhaust treated, e.g., de-ozonized, air into theatmosphere 181. Accordingly, this embodiment provides a gas, e.g., air,path from the interior of the vault to the exterior through a filtering(e.g., ozone and VOC filtering) system. In some embodiments the airinside the vault is recirculated. For example, an air conduit 280,depicted with dashed lines in FIG. 2, can optionally be added to thesystem to connect systems 170 and 180. In this way, purified air exitingsystem 180 could be recirculated through the vault via system 170 ratherthan being vented to the atmosphere. In some cases the vault can includeone or more recirculating loops of gas.

Air pollution control technologies can be used for the destruction ofprocess gases, for example, in manifold 182 and/or as part of system 180or anywhere therebetween, e.g. in the flow path between 180 and 182.Thermal oxidation can be utilized for the destruction of, for example,HAPs and VOCs. Since some HAPs and all VOCs are carbon based, thermaloxidizer systems can be used to destroy these gases by completeoxidation to carbon dioxide and water. Some types of thermal oxidizersystems, for example, that can be utilized to treat the process gases asdescribed herein, are regenerative thermal oxidizers, regenerativecatalytic oxidizers, thermal recuperative oxidizers and direct firedthermal oxidizer. The first three thermal oxidizer systems can bepreferable when designing for high energy efficiency because they allinclude some form of energy (e.g., heat) recovery and can have very highthermal efficiencies (e.g., greater than 95%). Air pollution controltechnologies for ozone generally include systems that convert ozone tooxygen. Other process gases, for example, NO_(x) can also be treatedwith ammonia to produced nitrogen and water. Filtering or abatementsystems for SF₆ gas can also be included in the systems to be includedin some embodiments of the invention.

Air pollution technologies often utilize a metal or metal oxidecatalyst. For example, metal and metal oxide catalysts (e.g., CuO—MnO₂,vanadium oxides, tungsten oxides, Pd and Pt). The catalysts allow theconversion reactions (e.g., to CO₂ and water, to O₂, to N₂ and water) tooccur at relatively lower temperatures, for example, at temperatures aslow as about 200 deg C. (e.g., 100 to 400 deg C.) lower than without thecatalysts). Air pollution technologies also often utilize activatedcarbon. Ozone can be reduced to oxygen directly utilizing an activatedcarbon filter (e.g., bed, column). Activated carbons also act as anadsorbent for VOCs and HAPs, selectively removing and holding the gaseson the surface until the carbon is regenerated. Activated carbons can beutilized in any useful form, for example, powdered carbon, granularcarbon, extruded carbon, bead carbon, impregnated carbon (for example,impregnated with iodine, silver and metal ions, e.g., Al, Mn, Zn, Fe,Li, Ca metal ions), polymer coated carbon, polymer supported carbon,acid washed carbon, high purity carbon, aerogel carbon, carbon clothand/or activated forms of these. The carbon can be designed/formed intodifferent configurations, for example, as a web filter, a pleatedfilter, a spiral filter, a layered filter, a packed column filter, andcombinations of these.

The catalysts and activated carbon as described herein can be utilizedin an any useful configuration, e.g., pelletized, extruded, supported(e.g., on silica, on alumina, on carbon, on graphite, onaluminosilicates, on clays, on a foam, on a sponge, on a mesh, on beads,on a honeycomb structure, on a ceramic, on a woven or non-woven cloth,on a pleated filter, on a spiral filter, on a layered filter), as amesh, as a wire, as fibers, in a column and/or on an filtering bed.

Optionally, process gases (e.g., components to be removed and/ordestroyed in the gas) can be concentrated using, for example, a rotorconcentrator and/or a centrifuge and then this concentrated gas streamcan be treated with the pollution control systems described herein.Concentration can provide the advantage of not requiring a highthroughput of gas through one of the air pollution control systems asdescribed herein, so that a smaller capacity (e.g., lower gas flow)system can be utilized. Optionally, the process gas stream can be splitinto two or more flows and each flow treated independently.

The air pollution technologies and systems can be utilized incombinations and in any order to treat the process gases. For example,systems for destruction and/or removal of VOCs and HAPs can be utilizedprior to ozone destruction systems. Additional systems can be utilized,for example, particulate filters, in combinations with these systems.Removal of particulates, then removal of VOCs and HAPs followed by Ozoneremoval can be preferred to reduce catalyst deactivation (e.g., foulingand catalyst poisoning can be reduced).

Some suppliers of process gas mitigation equipment (e.g., air pollutioncontrol technologies) and related supplies (e.g., filters, catalysts,activated carbon) include: Anguil Environmental Systems, Inc.(Milwaukee, Wis.); PureSphere Co., Inc. (Korea); General Air Products,Inc. (Exton, Pa.); Cabot Corp. (Boston, Mass.); Corporate ConsultingService Instruments, Inc. (Arkon, Ohio); Ozone Solutions, Inc. (Hull,Iowa); Columbus Industries, Inc. (Ashville, Ohio); California Carbon Co.Inc. (Wilmington, Calif.); Calgon Carbon Corporation (Pittsburgh, Pa.);and General Carbon Co. (Paterson, N.J.). Some specific ozone destructorunits that can be utilized in the methods described herein are; theNT-400 unit available from Auguil Environmental Systems Inc. and/orscaled up versions of this unit. An exemplary ozone destructor systemthat can be utilized in manifold 182 is the NT-400 or a scaled upversion of this system (e.g., so that high gas flow rates can beutilized), available from Ozone Solutions, Inc.

FIG. 3A is a detailed side view showing part of the process gasmitigation system including a system 200 for air-cooling window foils.In this air-cooling system, air entering the vault through conduit 140is blown through manifold 210 and directed into an enclosed area 212through conduit 178. The enclosed area 212 is positioned between thescan horn 128 and a conveyor system 132, which includes a trough 240 forcarrying biomass and a conveyor cover 242. The enclosed area 212 isdefined on one side by one or more foils 214 (e.g., titanium foils) onthe scanning horn, and on the other side by one or more foils 216 (e.g.,a window including titanium foil) mounted to the edges of an opening onthe conveyor cover 242. The foils on the scanning horn allow electronsfrom the high vacuum side 215 of the scanning horn to flow through thehigh pressure area between the foils 219 and to the atmospheric side217, as indicated by the “e⁻” arrows in FIG. 3A. Outlet 174 (and/or gap173 see FIG. 3B) is sized such that the pressure in the space 212 (highpressure area 219) is sufficient to keep the foils from fluttering inthe air flows therein. For example, the pressure in 219 is higher thanatmospheric pressure by at least about 0.1 psi, higher than atmosphericpressure by about 1 psi or from about 50-200 psig (e.g., about 75-200psig, about 80-150 psig). Foil 216 protects foil 214 from implosion,such as if particulates are projected towards the electron extractionwindows from the conveyor. For example, an outlet flow path, forexample, the outlet 174 and/or gap 173, can have a minimum crosssectional area perpendicular to the flow path of the gas (e.g., air,nitrogen, argon, helium) out of the space 212 that less than about 10%(e.g., less than about 20% the area, less than about 30% the area, lessthan about 40% the area, less than about 50% the area, less than about60% the area, less than about 70% the area, less than about 80% thearea) the minimum cross sectional area of the flow path of the gas intothe space 212 (e.g., through the opening of conduit 178). During biomasstreatment, electrons pass from the vacuum side 215 of the scanning horn,through foil 214, through the high pressure area 219, through foil 216and strike biomass 230 that is conveyed on conveyor surface (e.g.,trough) 240. Heat is generated during these electron interactions,necessitating cooling of the foils. The flow of air from manifold 210into the enclosed space assists with this cooling, maintaining efficientoperation of the scanning head. For example, cooled window foils andwindow foils integrated with conveyors.

As discussed above, the electron interaction with the biomass can reducethe recalcitrance of the biomass. Energy dissipation processes due tothe electrons striking the biomass or the conveyor surface can alsooccur. The heat produced, and/or the recalcitrance reduction of thebiomass, can release (e.g., create, volatilize) volatile organiccompounds (VOCs) and hazardous air pollutants (HAP), as indicated by the“VOC/HAP” arrow in FIG. 3A. Electrons can also interact with thecomponents of air, for example, dioxygen, producing toxic gases, e.g.,ozone. As shown in FIGS. 3A and 3B, ozone that is produced in theenclosed area 212 is vented out into the surrounding atmosphere, e.g.,the vault, by way of the gap 173 (FIG. 3B) and through outlet 174. Thegap 173 is defined by sheet (e.g., stainless steel sheet) 175 and sheet177 that are part of window cooling system and mounted to the manifold210. The gap 173 defines a conduit between the space 212 and the outlet174. The outlet 174 and manifold 210 are in fluid communication throughthe enclosure 212. FIG. 3C is a perspective view showing of the scanhorn, manifold 210 and outlet 174.

Some of the ozone generated during irradiation of biomass can react(e.g., oxidize) the biomass, while some of the ozone can leak out of theenclosed conveyor 132 into the vault. However, some ozone may be carriedout of the vault with the biomass. To control the ozone that exits thevault with the biomass, an ozone abatement system can be used, e.g., aclosed loop air conveyor with ozone abatement systems. For example,closed loop pneumatic conveyors and ozone abatement systems.

In some embodiments an inert gas, for example nitrogen, argon, carbondioxide, He, SF₆, SiF₄, CF₄, or mixtures thereof (e.g., more than about80% nitrogen, more than about 90% nitrogen, more than about 95%nitrogen, more than about 99% nitrogen), can be used to purge the vault.For example, with reference to FIG. 2 the inert gas is supplied to thevault through inlet 172. Processing the biomass in an atmosphere ofinert gas, rather than air, can reduce or even eliminate the formationof ozone. An inert gas can be supplied by a tank, transported from acentral location through a pipe and or generated close to theirradiation site. On site nitrogen generation technologies includemembrane technology (e.g., hollow fiber membrane technology) andpressure swing adsorption technologies. The inert gas can be recycled,as described for other gases by drawing the vault atmosphere throughmanifold 182, through system 180 and then coupling the flows 181 and171. Pressure adjustments and inert gas addition to compensate for anyloss can be done by systems such as 170 and 180 in addition toattachment to an inert gas compensation source (e.g., tank, supply influid communication with 170 and/or 180). Since the inert gas avoids theproduction of ozone no ozone destruction unit is necessary in thisoptional embodiment.

In some embodiments the pressure inside the vault is slightly lower thanthe pressure outside the vault. Ideally, the vault would be airtight sothat no process gases escape into the atmosphere, however this would inpractice be difficult to achieve. Thus, a similar result can be achievedby making the active flow out of the vault, and through a process gasabatement system, be higher than the air/gas made to flow into thevault, e.g., using system 170 as discussed above. For example, thepressure in the vault can be at least about 0.001% lower than thepressure outside of the vault (e.g., at least about 0.002% lower, atleast about 0.004% lower, at least about 0.006% lower, at least about0.008% lower, at least about 0.01% lower, at least about 0.05% lower, atleast about 0.1% lower, at least about 0.5% lower, at least about 1%lower, at least about 2% lower, at least about 5% lower, at least about10% lower, at least about 50% lower, or at least about 100% lower). Forexample, if the pressure outside of the vault is 1 atm, and the pressureinside the vault is at least 0.1% lower than the pressure outside thevault, then the pressure inside the vault is at least 0.9 atm or lower.The pressure differences can be achieved by controlling flow rate of airand/or gases into and out of the vault. For example, referring to FIG.2, by adjusting systems 170 and 180 so that the flow rate into the vaultat 171 is at a lower rate than the flow rate out of the vault at 181.For example, the flow rate at an outlet to the vault, flowing air out ofthe vault, can be at least 0.1 times the flow rate at an inlet to thevault, flowing air into the vault (e.g., at least 0.5 times, at least 1times, at least 2 times, at least 3 times, at least 4 times, at least 5times, at least 10 times, at least 50 times, at least 100 times, or atleast 200 times).

Some more details and reiterations of processes for treating a feedstockthat can be utilized, for example, with the embodiments alreadydiscussed above, or in other embodiments, are described in the followingdisclosures.

Radiation Treatment

The feedstock can be treated with radiation to modify its structure toreduce its recalcitrance. Such treatment can, for example, reduce theaverage molecular weight of the feedstock, change the crystallinestructure of the feedstock, and/or increase the surface area and/orporosity of the feedstock. Radiation can be by, for example, electronbeam, ion beam, 100 nm to 280 nm ultraviolet (UV) light, gamma or X-rayradiation. Radiation treatments and systems for treatments are discussedin U.S. Pat. No. 8,142,620 and U.S. patent application Ser. No.12/417,731, the entire disclosures of which are incorporated herein byreference.

Each form of radiation ionizes the biomass via particular interactions,as determined by the energy of the radiation. Heavy charged particlesprimarily ionize matter via Coulomb scattering; furthermore, theseinteractions produce energetic electrons that may further ionize matter.Alpha particles are identical to the nucleus of a helium atom and areproduced by the alpha decay of various radioactive nuclei, such asisotopes of bismuth, polonium, astatine, radon, francium, radium,several actinides, such as actinium, thorium, uranium, neptunium,curium, californium, americium, and plutonium. Electrons interact viaCoulomb scattering and bremsstrahlung radiation produced by changes inthe velocity of electrons.

When particles are utilized, they can be neutral (uncharged), positivelycharged or negatively charged. When charged, the charged particles canbear a single positive or negative charge, or multiple charges, e.g.,one, two, three or even four or more charges. In instances in whichchain scission is desired to change the molecular structure of thecarbohydrate containing material, positively charged particles may bedesirable, in part, due to their acidic nature. When particles areutilized, the particles can have the mass of a resting electron, orgreater, e.g., 500, 1000, 1500, or 2000 or more times the mass of aresting electron. For example, the particles can have a mass of fromabout 1 atomic unit to about 150 atomic units, e.g., from about 1 atomicunit to about 50 atomic units, or from about 1 to about 25, e.g., 1, 2,3, 4, 5, 10, 12 or 15 atomic units.

Gamma radiation has the advantage of a significant penetration depthinto a variety of material in the sample.

In embodiments in which the irradiating is performed withelectromagnetic radiation, the electromagnetic radiation can have, e.g.,energy per photon (in electron volts) of greater than 10² eV, e.g.,greater than 10³, 10⁴, 10⁵, 10⁶, or even greater than 10⁷ eV. In someembodiments, the electromagnetic radiation has energy per photon ofbetween 10⁴ and 10⁷, e.g., between 10⁵ and 10⁶ eV. The electromagneticradiation can have a frequency of, e.g., greater than 10¹⁶ Hz, greaterthan 10¹⁷ Hz, 10¹⁸, 10¹⁹, 10²⁰, or even greater than 10²¹ Hz. In someembodiments, the electromagnetic radiation has a frequency of between10¹⁸ and 10²² Hz, e.g., between 10¹⁹ to 10²¹ Hz.

Electron bombardment may be performed using an electron beam device thathas a nominal energy of less than 10 MeV, e.g., less than 7 MeV, lessthan 5 MeV, or less than 2 MeV, e.g., from about 0.5 to 1.5 MeV, fromabout 0.8 to 1.8 MeV, or from about 0.7 to 1 MeV. In someimplementations the nominal energy is about 500 to 800 keV.

The electron beam may have a relatively high total beam power (thecombined beam power of all accelerating heads, or, if multipleaccelerators are used, of all accelerators and all heads), e.g., atleast 25 kW, e.g., at least 30, 40, 50, 60, 65, 70, 80, 100, 125, or 150kW. In some cases, the power is even as high as 500 kW, 750 kW, or even1000 kW or more. In some cases the electron beam has a beam power of1200 kW or more, e.g., 1400, 1600, 1800, or even 3000 kW.

This high total beam power is usually achieved by utilizing multipleaccelerating heads. For example, the electron beam device may includetwo, four, or more accelerating heads. The use of multiple heads, eachof which has a relatively low beam power, prevents excessive temperaturerise in the material, thereby preventing burning of the material, andalso increases the uniformity of the dose through the thickness of thelayer of material.

It is generally preferred that the bed of biomass material has arelatively uniform thickness. In some embodiments the thickness is lessthan about 1 inch (e.g., less than about 0.75 inches, less than about0.5 inches, less than about 0.25 inches, less than about 0.1 inches,between about 0.1 and 1 inch, between about 0.2 and 0.3 inches).

It is desirable to treat the material as quickly as possible. Ingeneral, it is preferred that treatment be performed at a dose rate ofgreater than about 0.25 Mrad per second, e.g., greater than about 0.5,0.75, 1, 1.5, 2, 5, 7, 10, 12, 15, or even greater than about 20 Mradper second, e.g., about 0.25 to 2 Mrad per second. Higher dose ratesallow a higher throughput for a target (e.g., the desired) dose. Higherdose rates generally require higher line speeds, to avoid thermaldecomposition of the material. In one implementation, the accelerator isset for 3 MeV, 50 mA beam current, and the line speed is 24 feet/minute,for a sample thickness of about 20 mm (e.g., comminuted corn cobmaterial with a bulk density of 0.5 g/cm³).

In some embodiments, electron bombardment is performed until thematerial receives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad,5 Mrad, e.g., at least 10, 20, 30 or at least 40 Mrad. In someembodiments, the treatment is performed until the material receives adose of from about 10 Mrad to about 50 Mrad, e.g., from about 20 Mrad toabout 40 Mrad, or from about 25 Mrad to about 30 Mrad. In someimplementations, a total dose of 25 to 35 Mrad is preferred, appliedideally over a couple of passes, e.g., at 5 Mrad/pass with each passbeing applied for about one second. Cooling methods, systems andequipment can be used before, during, after and in between radiations,for example, utilizing a cooling screw conveyor and/or a cooledvibratory conveyor.

Using multiple heads as discussed above, the material can be treated inmultiple passes, for example, two passes at 10 to 20 Mrad/pass, e.g., 12to 18 Mrad/pass, separated by a few seconds of cool-down, or threepasses of 7 to 12 Mrad/pass, e.g., 5 to 20 Mrad/pass, 10 to 40Mrad/pass, 9 to 11 Mrad/pass. As discussed herein, treating the materialwith several relatively low doses, rather than one high dose, tends toprevent overheating of the material and also increases dose uniformitythrough the thickness of the material. In some implementations, thematerial is stirred or otherwise mixed during or after each pass andthen smoothed into a uniform layer again before the next pass, tofurther enhance treatment uniformity.

In some embodiments, electrons are accelerated to, for example, a speedof greater than 75 percent of the speed of light, e.g., greater than 85,90, 95, or 99 percent of the speed of light.

In some embodiments, any processing described herein occurs onlignocellulosic material that remains dry as acquired or that has beendried, e.g., using heat and/or reduced pressure. For example, in someembodiments, the cellulosic and/or lignocellulosic material has lessthan about 25 wt. % retained water, measured at 25° C. and at fiftypercent relative humidity (e.g., less than about 20 wt. %, less thanabout 15 wt. %, less than about 14 wt. %, less than about 13 wt. %, lessthan about 12 wt. %, less than about 10 wt. %, less than about 9 wt. %,less than about 8 wt. %, less than about 7 wt. %, less than about 6 wt.%, less than about 5 wt. %, less than about 4 wt. %, less than about 3wt. %, less than about 2 wt. %, less than about 1 wt. %, or less thanabout 0.5 wt. %.

In some embodiments, two or more ionizing sources can be used, such astwo or more electron sources. For example, samples can be treated, inany order, with a beam of electrons, followed by gamma radiation and UVlight having wavelengths from about 100 nm to about 280 nm. In someembodiments, samples are treated with three ionizing radiation sources,such as a beam of electrons, gamma radiation, and energetic UV light.The biomass is conveyed through the treatment zone where it can bebombarded with electrons.

It may be advantageous to repeat the treatment to more thoroughly reducethe recalcitrance of the biomass and/or further modify the biomass. Inparticular the process parameters can be adjusted after a first (e.g.,second, third, fourth or more) pass depending on the recalcitrance ofthe material. In some embodiments, a conveyor can be used which includesa circular system where the biomass is conveyed multiple times throughthe various processes described above. In some other embodimentsmultiple treatment devices (e.g., electron beam generators) are used totreat the biomass multiple (e.g., 2, 3, 4 or more) times. In yet otherembodiments, a single electron beam generator may be the source ofmultiple beams (e.g., 2, 3, 4 or more beams) that can be used fortreatment of the biomass.

The effectiveness in changing the molecular/supermolecular structureand/or reducing the recalcitrance of the carbohydrate-containing biomassdepends on the electron energy used and the dose applied, while exposuretime depends on the power and dose. In some embodiments, the dose rateand total dose are adjusted so as not to destroy (e.g., char or burn)the biomass material. For example, the carbohydrates should not bedamaged in the processing so that they can be released from the biomassintact, e.g. as monomeric sugars.

In some embodiments, the treatment (with any electron source or acombination of sources) is performed until the material receives a doseof at least about 0.05 Mrad, e.g., at least about 0.1, 0.25, 0.5, 0.75,1.0, 2.5, 5.0, 7.5, 10.0, 15, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100,125, 150, 175, or 200 Mrad. In some embodiments, the treatment isperformed until the material receives a dose of between 0.1-100 Mrad,1-200, 5-200, 10-200, 5-150, 50-150 Mrad, 5-100, 5-50, 5-40, 10-50,10-75, 15-50, 20-35 Mrad.

In some embodiments, relatively low doses of radiation are utilized,e.g., to increase the molecular weight of a cellulosic orlignocellulosic material (with any radiation source or a combination ofsources described herein). For example, a dose of at least about 0.05Mrad, e.g., at least about 0.1 Mrad or at least about 0.25, 0.5, 0.75.1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, or at least about 5.0 Mrad. In someembodiments, the irradiation is performed until the material receives adose of between 0.1 Mrad and 2.0 Mrad, e.g., between 0.5 Mrad and 4.0Mrad or between 1.0 Mrad and 3.0 Mrad.

It also can be desirable to irradiate from multiple directions,simultaneously or sequentially, in order to achieve a desired degree ofpenetration of radiation into the material. For example, depending onthe density and moisture content of the material, such as wood, and thetype of radiation source used (e.g., gamma or electron beam), themaximum penetration of radiation into the material may be only about0.75 inch. In such a cases, a thicker section (up to 1.5 inch) can beirradiated by first irradiating the material from one side, and thenturning the material over and irradiating from the other side.Irradiation from multiple directions can be particularly useful withelectron beam radiation, which irradiates faster than gamma radiationbut typically does not achieve as great a penetration depth.

Radiation Opaque Materials

As previously discussed, the invention can include processing thematerial in a vault and/or bunker that is constructed using radiationopaque materials. In some implementations, the radiation opaquematerials are selected to be capable of shielding the components fromX-rays with high energy (short wavelength), which can penetrate manymaterials. One important factor in designing a radiation shieldingenclosure is the attenuation length of the materials used, which willdetermine the required thickness for a particular material, blend ofmaterials, or layered structure. The attenuation length is thepenetration distance at which the radiation is reduced to approximately1/e (e=Euler's number) times that of the incident radiation. Althoughvirtually all materials are radiation opaque if thick enough, materialscontaining a high compositional percentage (e.g., density) of elementsthat have a high Z value (atomic number) have a shorter radiationattenuation length and thus if such materials are used a thinner,lighter shielding can be provided. Examples of high Z value materialsthat are used in radiation shielding are tantalum and lead. Anotherimportant parameter in radiation shielding is the halving distance,which is the thickness of a particular material that will reduce gammaray intensity by 50%. As an example for X-ray radiation with an energyof 0.1 MeV the halving thickness is about 15.1 mm for concrete and about2.7 mm for lead, while with an X-ray energy of 1 MeV the halvingthickness for concrete is about 44.45 mm and for lead is about 7.9 mm.Radiation opaque materials can be materials that are thick or thin solong as they can reduce the radiation that passes through to the otherside. Thus, if it is desired that a particular enclosure have a low wallthickness, e.g., for light weight or due to size constraints, thematerial chosen should have a sufficient Z value and/or attenuationlength so that its halving length is less than or equal to the desiredwall thickness of the enclosure.

In some cases, the radiation opaque material may be a layered material,for example having a layer of a higher Z value material, to provide goodshielding, and a layer of a lower Z value material to provide otherproperties (e.g., structural integrity, impact resistance, etc.). Insome cases, the layered material may be a “graded-Z” laminate, e.g.,including a laminate in which the layers provide a gradient from high-Zthrough successively lower-Z elements. In some cases the radiationopaque materials can be interlocking blocks, for example, lead and/orconcrete blocks can be supplied by NELCO Worldwide (Burlington, Mass.),and reconfigurable vaults can be utilized.

A radiation opaque material can reduce the radiation passing through astructure (e.g., a wall, door, ceiling, enclosure, a series of these orcombinations of these) formed of the material by about at least about10%, (e.g., at least about 20%, at least about 30%, at least about 40%,at least about 50%, at least about 60%, at least about 70%, at leastabout 80%, at least about 90%, at least about 95%, at least about 96%,at least about 97%, at least about 98%, at least about 99%, at leastabout 99.9%, at least about 99.99%, at least about 99.999%) as comparedto the incident radiation. Therefore, an enclosure made of a radiationopaque material can reduce the exposure of equipment/system/componentsby the same amount. Radiation opaque materials can include stainlesssteel, metals with Z values above 25 (e.g., lead, iron), concrete, dirt,sand and combinations thereof. Radiation opaque materials can include abarrier in the direction of the incident radiation of at least about 1mm (e.g., 5 mm, 10 mm, 5 cm, 10 cm, 100 cm, 1 m and even at least 10 m).

Radiation Sources

The type of radiation determines the kinds of radiation sources used aswell as the radiation devices and associated equipment. The methods,systems and equipment described herein, for example, for treatingmaterials with radiation, can utilized sources as described herein aswell as any other useful source.

Sources of gamma rays include radioactive nuclei, such as isotopes ofcobalt, calcium, technetium, chromium, gallium, indium, iodine, iron,krypton, samarium, selenium, sodium, thallium, and xenon.

Sources of X-rays include electron beam collision with metal targets,such as tungsten or molybdenum or alloys, or compact light sources, suchas those produced commercially by Lyncean.

Alpha particles are identical to the nucleus of a helium atom and areproduced by the alpha decay of various radioactive nuclei, such asisotopes of bismuth, polonium, astatine, radon, francium, radium,several actinides, such as actinium, thorium, uranium, neptunium,curium, californium, americium, and plutonium.

Sources for ultraviolet radiation include deuterium or cadmium lamps.

Sources for infrared radiation include sapphire, zinc, or selenidewindow ceramic lamps.

Sources for microwaves include klystrons, Slevin type RF sources, oratom beam sources that employ hydrogen, oxygen, or nitrogen gases.

Accelerators used to accelerate the particles (e.g., electrons or ions)can be DC (e.g., electrostatic DC or electrodynamic DC), RF linear,magnetic induction linear or continuous wave. For example, variousirradiating devices may be used in the methods disclosed herein,including field ionization sources, electrostatic ion separators, fieldionization generators, thermionic emission sources, microwave dischargeion sources, recirculating or static accelerators, dynamic linearaccelerators, van de Graaff accelerators, Cockroft Walton accelerators(e.g., PELLETRON® accelerators), LINACS, Dynamitrons (e.g., DYNAMITRON®accelerators), cyclotrons, synchrotrons, betatrons, transformer-typeaccelerators, microtrons, plasma generators, cascade accelerators, andfolded tandem accelerators. For example, cyclotron type accelerators areavailable from IBA, Belgium, such as the RHODOTRON™ system, while DCtype accelerators are available from RDI, now IBA Industrial, such asthe DYNAMITRON®. Other suitable accelerator systems include, forexample: DC insulated core transformer (ICT) type systems, availablefrom Nissin High Voltage, Japan; S-band LINACs, available from L3-PSD(USA), Linac Systems (France), Mevex (Canada), and Mitsubishi HeavyIndustries (Japan); L-band LINACs, available from Iotron Industries(Canada); and ILU-based accelerators, available from Budker Laboratories(Russia). Ions and ion accelerators are discussed in IntroductoryNuclear Physics, Kenneth S. Krane, John Wiley & Sons, Inc. (1988), KrstoPrelec, FIZIKA B 6 (1997) 4, 177-206, Chu, William T., “Overview ofLight-Ion Beam Therapy”, Columbus-Ohio, ICRU-IAEA Meeting, 18-20 Mar.2006, Iwata, Y. et al., “Alternating-Phase-Focused IH-DTL for Heavy-IonMedical Accelerators”, Proceedings of EPAC 2006, Edinburgh, Scotland,and Leitner, C. M. et al., “Status of the Superconducting ECR Ion SourceVenus”, Proceedings of EPAC 2000, Vienna, Austria. Some particleaccelerators and their uses are disclosed, for example, in U.S. Pat. No.7,931,784 to Medoff, the complete disclosure of which is incorporatedherein by reference.

Electrons may be produced by radioactive nuclei that undergo beta decay,such as isotopes of iodine, cesium, technetium, and iridium.Alternatively, an electron gun can be used as an electron source viathermionic emission and accelerated through an accelerating potential.An electron gun generates electrons, which are then accelerated througha large potential (e.g., greater than about 500 thousand, greater thanabout 1 million, greater than about 2 million, greater than about 5million, greater than about 6 million, greater than about 7 million,greater than about 8 million, greater than about 9 million, or evengreater than 10 million volts) and then scanned magnetically in the x-yplane, where the electrons are initially accelerated in the z directiondown the accelerator tube and extracted through a foil window. Scanningthe electron beams is useful for increasing the irradiation surface whenirradiating materials, e.g., a biomass, that is conveyed through thescanned beam. Scanning the electron beam also distributes the thermalload homogenously on the window and helps reduce the foil window rupturedue to local heating by the electron beam. Window foil rupture is acause of significant down-time due to subsequent necessary repairs andre-starting the electron gun.

Various other irradiating devices may be used in the methods disclosedherein, including field ionization sources, electrostatic ionseparators, field ionization generators, thermionic emission sources,microwave discharge ion sources, recirculating or static accelerators,dynamic linear accelerators, van de Graaff accelerators, and foldedtandem accelerators. Such devices are disclosed, for example, in U.S.Pat. No. 7,931,784 to Medoff, the complete disclosure of which isincorporated herein by reference.

A beam of electrons can be used as the radiation source. A beam ofelectrons has the advantages of high dose rates (e.g., 1, 5, or even 10Mrad per second), high throughput, less containment, and lessconfinement equipment. Electron beams can also have high electricalefficiency (e.g., 80%), allowing for lower energy usage relative toother radiation methods, which can translate into a lower cost ofoperation and lower greenhouse gas emissions corresponding to thesmaller amount of energy used. Electron beams can be generated, e.g., byelectrostatic generators, cascade generators, transformer generators,low energy accelerators with a scanning system, low energy acceleratorswith a linear cathode, linear accelerators, and pulsed accelerators.

Electrons can also be more efficient at causing changes in the molecularstructure of carbohydrate-containing materials, for example, by themechanism of chain scission. In addition, electrons having energies of0.5-10 MeV can penetrate low density materials, such as the biomassmaterials described herein, e.g., materials having a bulk density ofless than 0.5 g/cm³, and a depth of 0.3-10 cm. Electrons as an ionizingradiation source can be useful, e.g., for relatively thin piles, layersor beds of materials, e.g., less than about 0.5 inch, e.g., less thanabout 0.4 inch, 0.3 inch, 0.25 inch, or less than about 0.1 inch. Insome embodiments, the energy of each electron of the electron beam isfrom about 0.3 MeV to about 2.0 MeV (million electron volts), e.g., fromabout 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV.Methods of irradiating materials are discussed in U.S. Pat. App. Pub.2012/0100577 A1, filed Oct. 18, 2011, the entire disclosure of which isherein incorporated by reference.

Electron beam irradiation devices may be procured commercially or built.For example, elements or components such inductors, capacitors, casings,power sources, cables, wiring, voltage control systems, current controlelements, insulating material, microcontrollers and cooling equipmentcan be purchased and assembled into a device. Optionally, a commercialdevice can be modified and/or adapted. For example, devices andcomponents can be purchased from any of the commercial sources describedherein including Ion Beam Applications (Louvain-la-Neuve, Belgium),Wasik Associates Inc. (Dracut, Mass.), NHV Corporation (Japan), theTitan Corporation (San Diego, Calif.), Vivirad High Voltage Corp(Billerica, Mass.) and/or Budker Laboratories (Russia). Typical electronenergies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV, or 10 MeV.Typical electron beam irradiation device power can be 1 kW, 5 kW, 10 kW,20 kW, 50 kW, 60 kW, 70 kW, 80 kW, 90 kW, 100 kW, 125 kW, 150 kW, 175kW, 200 kW, 250 kW, 300 kW, 350 kW, 400 kW, 450 kW, 500 kW, 600 kW, 700kW, 800 kW, 900 kW or even 1000 kW. Accelerators that can be usedinclude NHV irradiators medium energy series EPS-500 (e.g., 500 kVaccelerator voltage and 65, 100 or 150 mA beam current), EPS-800 (e.g.,800 kV accelerator voltage and 65 or 100 mA beam current), or EPS-1000(e.g., 1000 kV accelerator voltage and 65 or 100 mA beam current). Also,accelerators from NHV's high energy series can be used such as EPS-1500(e.g., 1500 kV accelerator voltage and 65 mA beam current), EPS-2000(e.g., 2000 kV accelerator voltage and 50 mA beam current), EPS-3000(e.g., 3000 kV accelerator voltage and 50 mA beam current) and EPS-5000(e.g., 5000 and 30 mA beam current). Tradeoffs in considering electronbeam irradiation device power specifications include cost to operate,capital costs, depreciation, and device footprint. Tradeoffs inconsidering exposure dose levels of electron beam irradiation would beenergy costs and environment, safety, and health (ESH) concerns.Typically, generators are housed in a vault, e.g., of lead or concrete,especially for production from X-rays that are generated in the process.Tradeoffs in considering electron energies include energy costs.

The electron beam irradiation device can produce either a fixed beam ora scanning beam. A scanning beam may be advantageous with large scansweep length and high scan speeds, as this would effectively replace alarge, fixed beam width. Further, available sweep widths of 0.5 m, 1 m,2 m or more are available. The scanning beam is preferred in mostembodiments described herein because of the larger scan width andreduced possibility of local heating and failure of the windows.

Electron Guns—Windows

The extraction system for an electron accelerator can include two windowfoils. The cooling gas in the two foil window extraction system can be apurge gas or a mixture, for example, air, or a pure gas. In oneembodiment, the gas is an inert gas such as nitrogen, argon, heliumand/or carbon dioxide. It is preferred to use a gas rather than a liquidsince energy losses to the electron beam are minimized. Mixtures of puregas can also be used, either pre-mixed or mixed in line prior toimpinging on the windows or in the space between the windows. Thecooling gas can be cooled, for example, by using a heat exchange system(e.g., a chiller) and/or by using boil off from a condensed gas (e.g.,liquid nitrogen, liquid helium). Window foils are described inPCT/US2013/64332 filed Oct. 10, 2013 the full disclosure of which isincorporated by reference herein.

Heating and Throughput During Radiation Treatment

Several processes can occur in biomass when electrons from an electronbeam interact with matter in inelastic collisions. For example,ionization of the material, chain scission of polymers in the material,cross linking of polymers in the material, oxidation of the material,generation of X-rays (“Bremsstrahlung”) and vibrational excitation ofmolecules (e.g., phonon generation). Without being bound to a particularmechanism, the reduction in recalcitrance can be due to several of theseinelastic collision effects, for example, ionization, chain scission ofpolymers, oxidation and phonon generation. Some of the effects (e.g.,especially X-ray generation), necessitate shielding and engineeringbarriers, for example, enclosing the irradiation processes in a concrete(or other radiation opaque material) vault. Another effect ofirradiation, vibrational excitation, is equivalent to heating up thesample. Heating the sample by irradiation can help in recalcitrancereduction, but excessive heating can destroy the material, as will beexplained below.

The adiabatic temperature rise (ΔT) from adsorption of ionizingradiation is given by the equation: ΔT=D/Cp: where D is the average dosein kGy, Cp is the heat capacity in J/g ° C., and ΔT is the change intemperature in ° C. A typical dry biomass material will have a heatcapacity close to 2. Wet biomass will have a higher heat capacitydependent on the amount of water since the heat capacity of water isvery high (4.19 J/g ° C.). Metals have much lower heat capacities, forexample 304 stainless steel has a heat capacity of 0.5 J/g ° C. Thetemperature change due to the instant adsorption of radiation in abiomass and stainless steel for various doses of radiation is shown inTable 1. At the higher temperatures biomass will decompose causingextreme deviation from the estimated changes in temperature.

TABLE 1 Calculated Temperature increase for biomass and stainless steel.Dose (Mrad) Estimated Biomass ΔT (° C.) Steel ΔT (° C.) 10  50 200 50 250 (decomposed) 1000 100  500 (decomposed) 2000 150  750 (decomposed)3000 200 1000 (decomposed) 4000

High temperatures can destroy and/or modify the biopolymers in biomassso that the polymers (e.g., cellulose) are unsuitable for furtherprocessing. A biomass subjected to high temperatures can become dark,sticky and give off odors indicating decomposition. The stickiness caneven make the material hard to convey. The odors can be unpleasant andbe a safety issue. In fact, keeping the biomass below about 200° C. hasbeen found to be beneficial in the processes described herein (e.g.,below about 190° C., below about 180° C., below about 170° C., belowabout 160° C., below about 150° C., below about 140° C., below about130° C., below about 120° C., below about 110° C., between about 60° C.and 180° C., between about 60° C. and 160° C., between about 60° C. and150° C., between about 60° C. and 140° C., between about 60° C. and 130°C., between about 60° C. and 120° C., between about 80° C. and 180° C.,between about 100° C. and 180° C., between about 120° C. and 180° C.,between about 140° C. and 180° C., between about 160° C. and 180° C.,between about 100° C. and 140° C., between about 80° C. and 120° C.).

It has been found that irradiation above about 10 Mrad is desirable forthe processes described herein (e.g., reduction of recalcitrance). Ahigh throughput is also desirable so that the irradiation does notbecome a bottle neck in processing the biomass. The treatment isgoverned by a Dose rate equation: M=FP/D·time, where M is the mass ofirradiated material (kg), F is the fraction of power that is adsorbed(unit less), P is the emitted power (kW=Voltage in MeV×Current in mA),time is the treatment time (sec) and D is the adsorbed dose (kGy). In anexemplary process where the fraction of adsorbed power is fixed, thePower emitted is constant and a set dosage is desired, the throughput(e.g., M, the biomass processed) can be increased by increasing theirradiation time. However, increasing the irradiation time withoutallowing the material to cool, can excessively heat the material asexemplified by the calculations shown above. Since biomass has a lowthermal conductivity (less than about 0.1 Wm⁻¹K⁻¹), heat dissipation isslow, unlike, for example, metals (greater than about 10 Wm⁻¹K⁻¹) whichcan dissipate energy quickly as long as there is a heat sink to transferthe energy to.

Electron Guns—Beam Stops

In some embodiments the systems and methods include a beam stop (e.g., ashutter). For example, the beam stop can be used to quickly stop orreduce the irradiation of material without powering down the electronbeam device. Alternatively the beam stop can be used while powering upthe electron beam, e.g., the beam stop can stop the electron beam untila beam current of a desired level is achieved. The beam stop can beplaced between the primary foil window and a secondary foil window. Forexample, the beam stop can be mounted so that it is movable, that is, sothat it can be moved into and out of the beam path. Even partialcoverage of the beam can be used, for example, to control the dose ofirradiation. The beam stop can be mounted to the floor, to a conveyorfor the biomass, to a wall, to the radiation device (e.g., at the scanhorn), or to any structural support. Preferably the beam stop is fixedin relation to the scan horn so that the beam can be effectivelycontrolled by the beam stop. The beam stop can incorporate a hinge, arail, wheels, slots, or other means allowing for its operation in movinginto and out of the beam. The beam stop can be made of any material thatwill stop at least 5% of the electrons, e.g., at least 10%, 20%, 30%,40%, 50%, 60%, 70%, at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%,96%, 97%, 98%, 99% or even about 100% of the electrons.

The beam stop can be made of a metal including, but not limited to,stainless steel, lead, iron, molybdenum, silver, gold, titanium,aluminum, tin, or alloys of these, or laminates (layered materials) madewith such metals (e.g., metal-coated ceramic, metal-coated polymer,metal-coated composite, multilayered metal materials).

The beam stop can be cooled, for example, with a cooling fluid such asan aqueous solution or a gas. The beam stop can be partially orcompletely hollow, for example, with cavities. Interior spaces of thebeam stop can be used for cooling fluids and gases. The beam stop can beof any shape, including flat, curved, round, oval, square, rectangular,beveled and wedged shapes.

The beam stop can have perforations so as to allow some electronsthrough, thus controlling (e.g., reducing) the levels of radiationacross the whole area of the window, or in specific regions of thewindow. The beam stop can be a mesh formed, for example, from fibers orwires. Multiple beam stops can be used, together or independently, tocontrol the irradiation. The beam stop can be remotely controlled, e.g.,by radio signal or hard wired to a motor for moving the beam into or outof position.

Beam Dumps

The embodiments disclosed herein can also include a beam dump whenutilizing a radiation treatment. A beam dump's purpose is to safelyabsorb a beam of charged particles. Like a beam stop, a beam dump can beused to block the beam of charged particles. However, a beam dump ismuch more robust than a beam stop, and is intended to block the fullpower of the electron beam for an extended period of time. They areoften used to block the beam as the accelerator is powering up.

Beam dumps are also designed to accommodate the heat generated by suchbeams, and are usually made from materials such as copper, aluminum,carbon, beryllium, tungsten, or mercury. Beam dumps can be cooled, forexample, using a cooling fluid that can be in thermal contact with thebeam dump.

Biomass Materials

Lignocellulosic materials include, but are not limited to, wood,particle board, forestry wastes (e.g., sawdust, aspen wood, wood chips),grasses, (e.g., switchgrass, miscanthus, cord grass, reed canary grass),grain residues, (e.g., rice hulls, oat hulls, wheat chaff, barleyhulls), agricultural waste (e.g., silage, canola straw, wheat straw,barley straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal,abaca, corn cobs, corn stover, soybean stover, corn fiber, alfalfa, hay,coconut hair), sugar processing residues (e.g., bagasse, beet pulp,agave bagasse), algae, seaweed, manure, sewage, and mixtures of any ofthese.

In some cases, the lignocellulosic material includes corncobs. Ground orhammermilled corncobs can be spread in a layer of relatively uniformthickness for irradiation, and after irradiation are easy to disperse inthe medium for further processing. To facilitate harvest and collection,in some cases the entire corn plant is used, including the corn stalk,corn kernels, and in some cases even the root system of the plant.

Advantageously, no additional nutrients (other than a nitrogen source,e.g., urea or ammonia) are required during fermentation of corncobs orcellulosic or lignocellulosic materials containing significant amountsof corncobs.

Corncobs, before and after comminution, are also easier to convey anddisperse, and have a lesser tendency to form explosive mixtures in airthan other cellulosic or lignocellulosic materials such as hay andgrasses.

Cellulosic materials include, for example, paper, paper products, paperwaste, paper pulp, pigmented papers, loaded papers, coated papers,filled papers, magazines, printed matter (e.g., books, catalogs,manuals, labels, calendars, greeting cards, brochures, prospectuses,newsprint), printer paper, polycoated paper, card stock, cardboard,paperboard, materials having a high α-cellulose content such as cotton,and mixtures of any of these. For example, paper products as describedin U.S. application Ser. No. 13/396,365 (“Magazine Feedstocks” by Medoffet al., filed Feb. 14, 2012), the full disclosure of which isincorporated herein by reference.

Cellulosic materials can also include lignocellulosic materials whichhave been partially or fully de-lignified.

In some instances other biomass materials can be utilized, for example,starchy materials. Starchy materials include starch itself, e.g., cornstarch, wheat starch, potato starch or rice starch, a derivative ofstarch, or a material that includes starch, such as an edible foodproduct or a crop. For example, the starchy material can be arracacha,buckwheat, banana, barley, cassava, kudzu, ocra, sago, sorghum, regularhousehold potatoes, sweet potato, taro, yams, or one or more beans, suchas favas, lentils or peas. Blends of any two or more starchy materialsare also starchy materials. Mixtures of starchy, cellulosic and orlignocellulosic materials can also be used. For example, a biomass canbe an entire plant, a part of a plant or different parts of a plant,e.g., a wheat plant, cotton plant, a corn plant, rice plant or a tree.The starchy materials can be treated by any of the methods describedherein.

Microbial materials that can be used as feedstock can include, but arenot limited to, any naturally occurring or genetically modifiedmicroorganism or organism that contains or is capable of providing asource of carbohydrates (e.g., cellulose), for example, protists, e.g.,animal protists (e.g., protozoa such as flagellates, amoeboids,ciliates, and sporozoa) and plant protists (e.g., algae such alveolates,chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes,red algae, stramenopiles, and viridaeplantae). Other examples includeseaweed, plankton (e.g., macroplankton, mesoplankton, microplankton,nanoplankton, picoplankton, and femptoplankton), phytoplankton, bacteria(e.g., gram positive bacteria, gram negative bacteria, andextremophiles), yeast and/or mixtures of these. In some instances,microbial biomass can be obtained from natural sources, e.g., the ocean,lakes, bodies of water, e.g., salt water or fresh water, or on land.Alternatively or in addition, microbial biomass can be obtained fromculture systems, e.g., large scale dry and wet culture and fermentationsystems.

In other embodiments, the biomass materials, such as cellulosic, starchyand lignocellulosic feedstock materials, can be obtained from transgenicmicroorganisms and plants that have been modified with respect to a wildtype variety. Such modifications may be, for example, through theiterative steps of selection and breeding to obtain desired traits in aplant. Furthermore, the plants can have had genetic material removed,modified, silenced and/or added with respect to the wild type variety.For example, genetically modified plants can be produced by recombinantDNA methods, where genetic modifications include introducing ormodifying specific genes from parental varieties, or, for example, byusing transgenic breeding wherein a specific gene or genes areintroduced to a plant from a different species of plant and/or bacteria.Another way to create genetic variation is through mutation breedingwherein new alleles are artificially created from endogenous genes. Theartificial genes can be created by a variety of ways including treatingthe plant or seeds with, for example, chemical mutagens (e.g., usingalkylating agents, epoxides, alkaloids, peroxides, formaldehyde),irradiation (e.g., X-rays, gamma rays, neutrons, beta particles, alphaparticles, protons, deuterons, UV radiation) and temperature shocking orother external stressing and subsequent selection techniques. Othermethods of providing modified genes is through error prone PCR and DNAshuffling followed by insertion of the desired modified DNA into thedesired plant or seed. Methods of introducing the desired geneticvariation in the seed or plant include, for example, the use of abacterial carrier, biolistics, calcium phosphate precipitation,electroporation, gene splicing, gene silencing, lipofection,microinjection and viral carriers. Additional genetically modifiedmaterials have been described in U.S. application Ser. No. 13/396,369filed Feb. 14, 2012 the full disclosure of which is incorporated hereinby reference.

Any of the methods described herein can be practiced with mixtures ofany biomass materials described herein.

Other Materials

Other materials (e.g., natural or synthetic materials), for example,polymers, can be treated and/or made utilizing the methods, equipmentand systems described herein. For example, polyethylene (e.g., linearlow density ethylene and high density polyethylene), polystyrenes,sulfonated polystyrenes, poly (vinyl chloride), polyesters (e.g.,nylons, DACRON™, KODEL™), polyalkylene esters, poly vinyl esters,polyamides (e.g., KEVLAR™) polyethylene terephthalate, celluloseacetate, acetal, poly acrylonitrile, polycarbonates (LEXAN™), acrylics[e.g., poly (methyl methacrylate), poly(methyl methacrylate),polyacrylonitrile], Poly urethanes, polypropylene, poly butadiene,polyisobutylene, polyacrylonitrile, polychloroprene (e.g. neoprene),poly(cis-1,4-isoprene) [e.g., natural rubber], poly(trans-1,4-isoprene)[e.g., gutta percha], phenol formaldehyde, melamine formaldehyde,epoxides, polyesters, poly amines, polycarboxylic acids, polylacticacids, polyvinyl alcohols, polyanhydrides, poly fluoro carbons (e.g.,TEFLON™), silicons (e.g., silicone rubber), polysilanes, poly ethers(e.g., polyethylene oxide, polypropylene oxide), waxes, oils andmixtures of these. Also included are plastics, rubbers, elastomers,fibers, waxes, gels, oils, adhesives, thermoplastics, thermosets,biodegradable polymers, resins made with these polymers, other polymers,other materials and combinations thereof. The polymers can be made byany useful method including cationic polymerization, anionicpolymerization, radical polymerization, metathesis polymerization, ringopening polymerization, graft polymerization, addition polymerization.In some cases the treatments disclosed herein can be used, for example,for radically initiated graft polymerization and cross linking.Composites of polymers, for example, with glass, metals, biomass (e.g.,fibers, particles), ceramics can also be treated and/or made.

Other materials that can be treated by using the methods, systems andequipment disclosed herein are ceramic materials, minerals, metals,inorganic compounds. For example, silicon and germanium crystals,silicon nitrides, metal oxides, semiconductors, insulators, cements andor conductors.

In addition, manufactured multipart or shaped materials (e.g., molded,extruded, welded, riveted, layered or combined in any way) can betreated, for example, cables, pipes, boards, enclosures, integratedsemiconductor chips, circuit boards, wires, tires, windows, laminatedmaterials, gears, belts, machines, combinations of these. For example,treating a material by the methods described herein can modify thesurfaces, for example, making them susceptible to furtherfunctionalization, combinations (e.g., welding) and/or treatment cancross link the materials.

Biomass Material Preparation—Mechanical Treatments

The biomass can be in a dry form, for example, with less than about 35%moisture content (e.g., less than about 20%, less than about 15%, lessthan about 10% less than about 5%, less than about 4%, less than about3%, less than about 2% or even less than about 1%). The biomass can alsobe delivered in a wet state, for example as a wet solid, a slurry or asuspension with at least about 10 wt. % solids (e.g., at least about 20wt. %, at least about 30 wt. %, at least about 40 wt. %, at least about50 wt. %, at least about 60 wt. %, at least about 70 wt. %).

The processes disclosed herein can utilize low bulk density materials,for example cellulosic or lignocellulosic feedstocks that have beenphysically pretreated to have a bulk density of less than about 0.75g/cm³, e.g., less than about 0.7, 0.65, 0.60, 0.50, 0.35, 0.25, 0.20,0.15, 0.10, 0.05 or less, e.g., less than about 0.025 g/cm³. Bulkdensity is determined using ASTM D1895B. Briefly, the method involvesfilling a measuring cylinder of known volume with a sample and obtaininga weight of the sample. The bulk density is calculated by dividing theweight of the sample in grams by the known volume of the cylinder incubic centimeters. If desired, low bulk density materials can bedensified, for example, by methods described in U.S. Pat. No. 7,971,809to Medoff, the full disclosure of which is hereby incorporated byreference.

In some cases, the pre-treatment processing includes screening of thebiomass material. Screening can be through a mesh or perforated platewith a desired opening size, for example, less than about 6.35 mm (¼inch, 0.25 inch), (e.g., less than about 3.18 mm (⅛ inch, 0.125 inch),less than about 1.59 mm ( 1/16 inch, 0.0625 inch), is less than about0.79 mm ( 1/32 inch, 0.03125 inch), e.g., less than about 0.51 mm ( 1/50inch, 0.02000 inch), less than about 0.40 mm ( 1/64 inch, 0.015625inch), less than about 0.23 mm (0.009 inch), less than about 0.20 mm (1/128 inch, 0.0078125 inch), less than about 0.18 mm (0.007 inch), lessthan about 0.13 mm (0.005 inch), or even less than about 0.10 mm ( 1/256inch, 0.00390625 inch)). In one configuration the desired biomass fallsthrough the perforations or screen and thus biomass larger than theperforations or screen are not irradiated. These larger materials can bere-processed, for example, by comminuting, or they can simply be removedfrom processing. In another configuration material that is larger thanthe perforations is irradiated and the smaller material is removed bythe screening process or recycled. In this kind of a configuration, theconveyor itself (for example, a part of the conveyor) can be perforatedor made with a mesh. For example, in one particular embodiment thebiomass material may be wet and the perforations or mesh allow water todrain away from the biomass before irradiation.

Screening of material can also be by a manual method, for example, by anoperator or mechanoid (e.g., a robot equipped with a color, reflectivityor other sensor) that removes unwanted material. Screening can also beby magnetic screening wherein a magnet is disposed near the conveyedmaterial and the magnetic material is removed magnetically.

Optional pre-treatment processing can include heating the material. Forexample, a portion of a conveyor conveying the biomass or other materialcan be sent through a heated zone. The heated zone can be created, forexample, by IR radiation, microwaves, combustion (e.g., gas, coal, oil,biomass), resistive heating and/or inductive coils. The heat can beapplied from at least one side or more than one side, can be continuousor periodic and can be for only a portion of the material or all thematerial. For example, a portion of the conveying trough can be heatedby use of a heating jacket. Heating can be, for example, for the purposeof drying the material. In the case of drying the material, this canalso be facilitated, with or without heating, by the movement of a gas(e.g., air, oxygen, nitrogen, He, CO₂, Argon) over and/or through thebiomass as it is being conveyed.

Optionally, pre-treatment processing can include cooling the material.Cooling material is described in U.S. Pat. No. 7,900,857 to Medoff, thedisclosure of which in incorporated herein by reference. For example,cooling can be by supplying a cooling fluid, for example, water (e.g.,with glycerol), or nitrogen (e.g., liquid nitrogen) to the bottom of theconveying trough. Alternatively, a cooling gas, for example, chillednitrogen can be blown over the biomass materials or under the conveyingsystem.

Another optional pre-treatment processing method can include adding amaterial to the biomass or other feedstocks. The additional material canbe added by, for example, by showering, sprinkling and or pouring thematerial onto the biomass as it is conveyed. Materials that can be addedinclude, for example, metals, ceramics and/or ions as described in U.S.Pat. App. Pub. 2010/0105119 A1 (filed Oct. 26, 2009) and U.S. Pat. App.Pub. 2010/0159569 A1 (filed Dec. 16, 2009), the entire disclosures ofwhich are incorporated herein by reference. Optional materials that canbe added include acids and bases. Other materials that can be added areoxidants (e.g., peroxides, chlorates), polymers, polymerizable monomers(e.g., containing unsaturated bonds), water, catalysts, enzymes and/ororganisms. Materials can be added, for example, in pure form, as asolution in a solvent (e.g., water or an organic solvent) and/or as asolution. In some cases the solvent is volatile and can be made toevaporate e.g., by heating and/or blowing gas as previously described.The added material may form a uniform coating on the biomass or be ahomogeneous mixture of different components (e.g., biomass andadditional material). The added material can modulate the subsequentirradiation step by increasing the efficiency of the irradiation,damping the irradiation or changing the effect of the irradiation (e.g.,from electron beams to X-rays or heat). The method may have no impact onthe irradiation but may be useful for further downstream processing. Theadded material may help in conveying the material, for example, bylowering dust levels.

Biomass can be delivered to a conveyor (e.g., vibratory conveyors thatcan be used in the vaults herein described) by a belt conveyor, apneumatic conveyor, a screw conveyor, a hopper, a pipe, manually or by acombination of these. The biomass can, for example, be dropped, pouredand/or placed onto the conveyor by any of these methods. In someembodiments the material is delivered to the conveyor using an enclosedmaterial distribution system to help maintain a low oxygen atmosphereand/or control dust and fines. Lofted or air suspended biomass fines anddust are undesirable because these can form an explosion hazard ordamage the window foils of an electron gun (if such a device is used fortreating the material).

The material can be leveled to form a uniform thickness between about0.0312 and 5 inches (e.g., between about 0.0625 and 2.000 inches,between about 0.125 and 1 inches, between about 0.125 and 0.5 inches,between about 0.3 and 0.9 inches, between about 0.2 and 0.5 inchesbetween about 0.25 and 1.0 inches, between about 0.25 and 0.5 inches,0.100+/−0.025 inches, 0.150+/−0.025 inches, 0.200+/−0.025 inches,0.250+/−0.025 inches, 0.300+/−0.025 inches, 0.350+/−0.025 inches,0.400+/−0.025 inches, 0.450+/−0.025 inches, 0.500+/−0.025 inches,0.550+/−0.025 inches, 0.600+/−0.025 inches, 0.700+/−0.025 inches,0.750+/−0.025 inches, 0.800+/−0.025 inches, 0.850+/−0.025 inches,0.900+/−0.025 inches, 0.900+/−0.025 inches.

Generally, it is preferred to convey the material as quickly as possiblethrough the electron beam to maximize throughput. For example, thematerial can be conveyed at rates of at least 1 ft/min, e.g., at least 2ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, atleast 10 ft/min, at least 15 ft/min, 20, 25, 30, 35, 40, 45, 50 ft/min.The rate of conveying is related to the beam current, for example, for a¼ inch thick biomass and 100 mA, the conveyor can move at about 20ft/min to provide a useful irradiation dosage, at 50 mA the conveyor canmove at about 10 ft/min to provide approximately the same irradiationdosage.

After the biomass material has been conveyed through the radiation zone,optional post-treatment processing can be done. The optionalpost-treatment processing can, for example, be a process described withrespect to the pre-irradiation processing. For example, the biomass canbe screened, heated, cooled, and/or combined with additives. Uniquely topost-irradiation, quenching of the radicals can occur, for example, bythe addition of fluids or gases (e.g., oxygen, nitrous oxide, ammoniaand/or liquids), using pressure, heat, and/or the addition of radicalscavengers. For example, the biomass can be conveyed out of the enclosedconveyor and exposed to a gas (e.g., oxygen) where it is quenched,forming carboxylated groups. In one embodiment, the biomass is exposedduring irradiation to the reactive gas or fluid. Quenching of biomassthat has been irradiated is described in U.S. Pat. No. 8,083,906 toMedoff, the entire disclosure of which is incorporate herein byreference.

If desired, one or more mechanical treatments can be used in addition toirradiation to further reduce the recalcitrance of thecarbohydrate-containing material. These processes can be applied before,during and/or after irradiation.

In some cases, the mechanical treatment may include an initialpreparation of the feedstock as received, e.g., size reduction ofmaterials, such as by comminution, e.g., cutting, grinding, shearing,pulverizing or chopping. For example, in some cases, loose feedstock(e.g., recycled paper, starchy materials, or switchgrass) is prepared byshearing or shredding. Mechanical treatment may reduce the bulk densityof the carbohydrate-containing material, increase the surface area ofthe carbohydrate-containing material and/or decrease one or moredimensions of the carbohydrate-containing material.

Alternatively, or in addition, the feedstock material can be treatedwith another treatment, for example, chemical treatments, such as anacid (HCl, H₂SO₄, H₃PO₄), a base (e.g., KOH and NaOH), a chemicaloxidant (e.g., peroxides, chlorates, ozone), irradiation, steamexplosion, pyrolysis, sonication, oxidation, chemical treatment. Thetreatments can be in any order and in any sequence and combinations. Forexample, the feedstock material can first be physically treated by oneor more treatment methods, e.g., chemical treatment including and incombination with acid hydrolysis (e.g., utilizing HCl, H₂SO₄, H₃PO₄),radiation, sonication, oxidation, pyrolysis or steam explosion, and thenmechanically treated. This sequence can be advantageous since materialstreated by one or more of the other treatments, e.g., irradiation orpyrolysis, tend to be more brittle and, therefore, it may be easier tofurther change the structure of the material by mechanical treatment. Asanother example, a feedstock material can be conveyed through ionizingradiation using a conveyor as described herein and then mechanicallytreated. Chemical treatment can remove some or all of the lignin (forexample, chemical pulping) and can partially or completely hydrolyze thematerial. The methods also can be used with pre-hydrolyzed material. Themethods also can be used with material that has not been pre-hydrolyzed.The methods can be used with mixtures of hydrolyzed and non-hydrolyzedmaterials, for example, with about 50% or more non-hydrolyzed material,with about 60% or more non-hydrolyzed material, with about 70% or morenon-hydrolyzed material, with about 80% or more non-hydrolyzed materialor even with 90% or more non-hydrolyzed material.

In addition to size reduction, which can be performed initially and/orlater in processing, mechanical treatment can also be advantageous for“opening up,” “stressing,” breaking or shattering thecarbohydrate-containing materials, making the cellulose of the materialsmore susceptible to chain scission and/or disruption of crystallinestructure during the physical treatment.

Methods of mechanically treating the carbohydrate-containing materialinclude, for example, milling or grinding. Milling may be performedusing, for example, a hammer mill, ball mill, colloid mill, conical orcone mill, disk mill, edge mill, Wiley mill, grist mill or other mill.Grinding may be performed using, for example, a cutting/impact typegrinder. Some exemplary grinders include stone grinders, pin grinders,coffee grinders, and burr grinders. Grinding or milling may be provided,for example, by a reciprocating pin or other element, as is the case ina pin mill. Other mechanical treatment methods include mechanicalripping or tearing, other methods that apply pressure to the fibers, andair attrition milling. Suitable mechanical treatments further includeany other technique that continues the disruption of the internalstructure of the material that was initiated by the previous processingsteps.

Mechanical feed preparation systems can be configured to produce streamswith specific characteristics such as, for example, specific maximumsizes, specific length-to-width, or specific surface areas ratios.Physical preparation can increase the rate of reactions, improve themovement of material on a conveyor, improve the irradiation profile ofthe material, improve the radiation uniformity of the material, orreduce the processing time required by opening up the materials andmaking them more accessible to processes and/or reagents, such asreagents in a solution.

The bulk density of feedstocks can be controlled (e.g., increased). Insome situations, it can be desirable to prepare a low bulk densitymaterial, e.g., by densifying the material (e.g., densification can makeit easier and less costly to transport to another site) and thenreverting the material to a lower bulk density state (e.g., aftertransport). The material can be densified, for example, from less thanabout 0.2 g/cc to more than about 0.9 g/cc (e.g., less than about 0.3 tomore than about 0.5 g/cc, less than about 0.3 to more than about 0.9g/cc, less than about 0.5 to more than about 0.9 g/cc, less than about0.3 to more than about 0.8 g/cc, less than about 0.2 to more than about0.5 g/cc). For example, the material can be densified by the methods andequipment disclosed in U.S. Pat. No. 7,932,065 to Medoff andInternational Publication No. WO 2008/073186 (which was filed Oct. 26,2007, was published in English, and which designated the United States),the full disclosures of which are incorporated herein by reference.Densified materials can be processed by any of the methods describedherein, or any material processed by any of the methods described hereincan be subsequently densified.

In some embodiments, the material to be processed is in the form of afibrous material that includes fibers provided by shearing a fibersource. For example, the shearing can be performed with a rotary knifecutter.

For example, a fiber source, e.g., that is recalcitrant or that has hadits recalcitrance level reduced, can be sheared, e.g., in a rotary knifecutter, to provide a first fibrous material. The first fibrous materialis passed through a first screen, e.g., having an average opening sizeof 1.59 mm or less ( 1/16 inch, 0.0625 inch), provide a second fibrousmaterial. If desired, the fiber source can be cut prior to the shearing,e.g., with a shredder. For example, when a paper is used as the fibersource, the paper can be first cut into strips that are, e.g., ¼-to½-inch wide, using a shredder, e.g., a counter-rotating screw shredder,such as those manufactured by Munson (Utica, N.Y.). As an alternative toshredding, the paper can be reduced in size by cutting to a desired sizeusing a guillotine cutter. For example, the guillotine cutter can beused to cut the paper into sheets that are, e.g., 10 inches wide by 12inches long.

In some embodiments, the shearing of the fiber source and the passing ofthe resulting first fibrous material through a first screen areperformed concurrently. The shearing and the passing can also beperformed in a batch-type process.

For example, a rotary knife cutter can be used to concurrently shear thefiber source and screen the first fibrous material. A rotary knifecutter includes a hopper that can be loaded with a shredded fiber sourceprepared by shredding a fiber source.

In some implementations, the feedstock is physically treated prior tosaccharification and/or fermentation. Physical treatment processes caninclude one or more of any of those described herein, such as mechanicaltreatment, chemical treatment, irradiation, sonication, oxidation,pyrolysis or steam explosion. Treatment methods can be used incombinations of two, three, four, or even all of these technologies (inany order). When more than one treatment method is used, the methods canbe applied at the same time or at different times. Other processes thatchange a molecular structure of a biomass feedstock may also be used,alone or in combination with the processes disclosed herein.

Mechanical treatments that may be used, and the characteristics of themechanically treated carbohydrate-containing materials, are described infurther detail in U.S. Pat. App. Pub. 2012/0100577 A1, filed Oct. 18,2011, the full disclosure of which is hereby incorporated herein byreference.

Sonication, Pyrolysis, Oxidation, Steam Explosion

If desired, one or more sonication, pyrolysis, oxidative, or steamexplosion processes can be used, instead of or in addition to,irradiation to reduce or further reduce the recalcitrance of thecarbohydrate-containing material. For example, these processes can beapplied before, during and/or after irradiation. These processes aredescribed in detail in U.S. Pat. No. 7,932,065 to Medoff, the fulldisclosure of which is incorporated herein by reference.

Intermediates and Products

Using the processes described herein, the biomass material can beconverted to one or more products, such as energy, fuels, foods andmaterials. For example, intermediates and products such as organicacids, salts of organic acids, anhydrides, esters of organic acids andfuels, e.g., fuels for internal combustion engines or feedstocks forfuel cells. Systems and processes are described herein that can use asfeedstock cellulosic and/or lignocellulosic materials that are readilyavailable, but often can be difficult to process, e.g., municipal wastestreams and waste paper streams, such as streams that include newspaper,Kraft paper, corrugated paper or mixtures of these.

Specific examples of products include, but are not limited to, hydrogen,sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose,disaccharides, oligosaccharides and polysaccharides), alcohols (e.g.,monohydric alcohols or dihydric alcohols, such as ethanol, n-propanol,isobutanol, sec-butanol, tert-butanol or n-butanol), hydrated or hydrousalcohols (e.g., containing greater than 10%, 20%, 30% or even greaterthan 40% water), biodiesel, organic acids, hydrocarbons (e.g., methane,ethane, propane, isobutene, pentane, n-hexane, biodiesel, bio-gasolineand mixtures thereof), co-products (e.g., proteins, such as cellulolyticproteins (enzymes) or single cell proteins), and mixtures of any ofthese in any combination or relative concentration, and optionally, incombination with any additives (e.g., fuel additives). Other examplesinclude carboxylic acids, salts of a carboxylic acid, a mixture ofcarboxylic acids and salts of carboxylic acids and esters of carboxylicacids (e.g., methyl, ethyl and n-propyl esters), ketones (e.g.,acetone), aldehydes (e.g., acetaldehyde), alpha and beta unsaturatedacids (e.g., acrylic acid) and olefins (e.g., ethylene). Other alcoholsand alcohol derivatives include propanol, propylene glycol,1,4-butanediol, 1,3-propanediol, sugar alcohols (e.g., erythritol,glycol, glycerol, sorbitol threitol, arabitol, ribitol, mannitol,dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol andother polyols), and methyl or ethyl esters of any of these alcohols.Other products include methyl acrylate, methylmethacrylate, D-lacticacid, L-lactic acid, pyruvic acid, poly lactic acid, citric acid, formicacid, acetic acid, propionic acid, butyric acid, succinic acid, valericacid, caproic acid, 3-hydroxypropionic acid, palmitic acid, stearicacid, oxalic acid, malonic acid, glutaric acid, oleic acid, linoleicacid, glycolic acid, gamma-hydroxybutyric acid, and mixtures thereof,salts of any of these acids, mixtures of any of the acids and theirrespective salts.

Any combination of the above products with each other, and/or of theabove products with other products, which other products may be made bythe processes described herein or otherwise, may be packaged togetherand sold as products. The products may be combined, e.g., mixed, blendedor co-dissolved, or may simply be packaged or sold together.

Any of the products or combinations of products described herein may besanitized or sterilized prior to selling the products, e.g., afterpurification or isolation or even after packaging, to neutralize one ormore potentially undesirable contaminants that could be present in theproduct(s). Such sanitation can be done with electron bombardment, forexample, be at a dosage of less than about 20 Mrad, e.g., from about 0.1to 15 Mrad, from about 0.5 to 7 Mrad, or from about 1 to 3 Mrad.

The processes described herein can produce various by-product streamsuseful for generating steam and electricity to be used in other parts ofthe plant (co-generation) or sold on the open market. For example, steamgenerated from burning by-product streams can be used in a distillationprocess. As another example, electricity generated from burningby-product streams can be used to power electron beam generators used inpretreatment.

The by-products used to generate steam and electricity are derived froma number of sources throughout the process. For example, anaerobicdigestion of wastewater can produce a biogas high in methane and a smallamount of waste biomass (sludge). As another example,post-saccharification and/or post-distillate solids (e.g., unconvertedlignin, cellulose, and hemicellulose remaining from the pretreatment andprimary processes) can be used, e.g., burned, as a fuel.

Other intermediates and products, including food and pharmaceuticalproducts, are described in U.S. Pat. App. Pub. 2010/0124583 A1,published May 20, 2010, to Medoff, the full disclosure of which ishereby incorporated by reference herein.

Lignin Derived Products

The spent biomass (e.g., spent lignocellulosic material) fromlignocellulosic processing by the methods described are expected to havea high lignin content and in addition to being useful for producingenergy through combustion in a Co-Generation plant, may have uses asother valuable products. For example, the lignin can be used as capturedas a plastic, or it can be synthetically upgraded to other plastics. Insome instances, it can also be converted to lignosulfonates, which canbe utilized as binders, dispersants, emulsifiers or sequestrants.

When used as a binder, the lignin or a lignosulfonate can, e.g., beutilized in coal briquettes, in ceramics, for binding carbon black, forbinding fertilizers and herbicides, as a dust suppressant, in the makingof plywood and particle board, for binding animal feeds, as a binder forfiberglass, as a binder in linoleum paste and as a soil stabilizer.

When used as a dispersant, the lignin or lignosulfonates can be used,for example in, concrete mixes, clay and ceramics, dyes and pigments,leather tanning and in gypsum board.

When used as an emulsifier, the lignin or lignosulfonates can be used,e.g., in asphalt, pigments and dyes, pesticides and wax emulsions.

As a sequestrant, the lignin or lignosulfonates can be used, e.g., inmicro-nutrient systems, cleaning compounds and water treatment systems,e.g., for boiler and cooling systems.

For energy production lignin generally has a higher energy content thanholocellulose (cellulose and hemicellulose) since it contains morecarbon than homocellulose. For example, dry lignin can have an energycontent of between about 11,000 and 12,500 BTU per pound, compared to7,000 an 8,000 BTU per pound of holocellulose. As such, lignin can bedensified and converted into briquettes and pellets for burning. Forexample, the lignin can be converted into pellets by any methoddescribed herein. For a slower burning pellet or briquette, the lignincan be crosslinked, such as applying a radiation dose of between about0.5 Mrad and 5 Mrad. Crosslinking can make a slower burning form factor.The form factor, such as a pellet or briquette, can be converted to a“synthetic coal” or charcoal by pyrolyzing in the absence of air, e.g.,at between 400 and 950° C. Prior to pyrolyzing, it can be desirable tocrosslink the lignin to maintain structural integrity.

Saccharification

In order to convert the feedstock to a form that can be readilyprocessed, the glucan- or xylan-containing cellulose in the feedstockcan be hydrolyzed to low molecular weight carbohydrates, such as sugars,by a saccharifying agent, e.g., an enzyme or acid, a process referred toas saccharification. The low molecular weight carbohydrates can then beused, for example, in an existing manufacturing plant, such as a singlecell protein plant, an enzyme manufacturing plant, or a fuel plant,e.g., an ethanol manufacturing facility.

The feedstock can be hydrolyzed using an enzyme, e.g., by combining thematerials and the enzyme in a solvent, e.g., in an aqueous solution.

Alternatively, the enzymes can be supplied by organisms that break downbiomass, such as the cellulose and/or the lignin portions of thebiomass, contain or manufacture various cellulolytic enzymes(cellulases), ligninases or various small molecule biomass-degradingmetabolites. These enzymes may be a complex of enzymes that actsynergistically to degrade crystalline cellulose or the lignin portionsof biomass. Examples of cellulolytic enzymes include: endoglucanases,cellobiohydrolases, and cellobiases (beta-glucosidases).

During saccharification, a cellulosic substrate can be initiallyhydrolyzed by endoglucanases at random locations producing oligomericintermediates. These intermediates are then substrates for exo-splittingglucanases such as cellobiohydrolase to produce cellobiose from the endsof the cellulose polymer. Cellobiose is a water-soluble 1,4-linked dimerof glucose. Finally, cellobiase cleaves cellobiose to yield glucose. Theefficiency (e.g., time to hydrolyze and/or completeness of hydrolysis)of this process depends on the recalcitrance of the cellulosic material.

Therefore, the treated biomass materials can be saccharified, generallyby combining the material and a cellulase enzyme in a fluid medium,e.g., an aqueous solution. In some cases, the material is boiled,steeped, or cooked in hot water prior to saccharification, as describedin U.S. Pat. App. Pub. 2012/0100577 A1 by Medoff and Masterman,published on Apr. 26, 2012, the entire contents of which areincorporated herein.

The saccharification process can be partially or completely performed ina tank (e.g., a tank having a volume of at least 4000, 40,000, or500,000 L) in a manufacturing plant, and/or can be partially orcompletely performed in transit, e.g., in a rail car, tanker truck, orin a supertanker or the hold of a ship. The time required for completesaccharification will depend on the process conditions and thecarbohydrate-containing material and enzyme used. If saccharification isperformed in a manufacturing plant under controlled conditions, thecellulose may be substantially entirely converted to sugar, e.g.,glucose in about 12-96 hours. If saccharification is performed partiallyor completely in transit, saccharification may take longer.

It is generally preferred that the tank contents be mixed duringsaccharification, e.g., using jet mixing as described in InternationalApp. No. PCT/US2010/035331, filed May 18, 2010, which was published inEnglish as WO 2010/135380 and designated the United States, the fulldisclosure of which is incorporated by reference herein.

The addition of surfactants can enhance the rate of saccharification.Examples of surfactants include non-ionic surfactants, such as a Tween®20 or Tween® 80 polyethylene glycol surfactants, ionic surfactants, oramphoteric surfactants.

It is generally preferred that the concentration of the sugar solutionresulting from saccharification be relatively high, e.g., greater than40%, or greater than 50, 60, 70, 80, 90 or even greater than 95% byweight. Water may be removed, e.g., by evaporation, to increase theconcentration of the sugar solution. This reduces the volume to beshipped, and also inhibits microbial growth in the solution.

Alternatively, sugar solutions of lower concentrations may be used, inwhich case it may be desirable to add an antimicrobial additive, e.g., abroad spectrum antibiotic, in a low concentration, e.g., 50 to 150 ppm.Other suitable antibiotics include amphotericin B, ampicillin,chloramphenicol, ciprofloxacin, gentamicin, hygromycin B, kanamycin,neomycin, penicillin, puromycin, streptomycin. Antibiotics will inhibitgrowth of microorganisms during transport and storage, and can be usedat appropriate concentrations, e.g., between 15 and 1000 ppm by weight,e.g., between 25 and 500 ppm, or between 50 and 150 ppm. If desired, anantibiotic can be included even if the sugar concentration is relativelyhigh. Alternatively, other additives with anti-microbial preservativeproperties may be used. Preferably the antimicrobial additive(s) arefood-grade.

A relatively high concentration solution can be obtained by limiting theamount of water added to the carbohydrate-containing material with theenzyme. The concentration can be controlled, e.g., by controlling howmuch saccharification takes place. For example, concentration can beincreased by adding more carbohydrate-containing material to thesolution. In order to keep the sugar that is being produced in solution,a surfactant can be added, e.g., one of those discussed above.Solubility can also be increased by increasing the temperature of thesolution. For example, the solution can be maintained at a temperatureof 40-50° C., 60-80° C., or even higher.

Saccharifying Agents

Suitable cellulolytic enzymes include cellulases from species in thegenera Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium,Penicillium, Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia,Acremonium, Chrysosporium and Trichoderma, especially those produced bya strain selected from the species Aspergillus (see, e.g., EP Pub. No. 0458 162), Humicola insolens (reclassified as Scytalidium thermophilum,see, e.g., U.S. Pat. No. 4,435,307), Coprinus cinereus, Fusariumoxysporum, Myceliophthora thermophila, Meripilus giganteus, Thielaviaterrestris, Acremonium sp. (including, but not limited to, A.persicinum, A. acremonium, A. brachypenium, A. dichromosporum, A.obclavatum, A. pinkertoniae, A. roseogriseum, A. incoloratum, and A.furatum). Preferred strains include Humicola insolens DSM 1800, Fusariumoxysporum DSM 2672, Myceliophthora thermophila CBS 117.65,Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp.CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium AHU9519, Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73,Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74,Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56,Acremonium incoloratum CBS 146.62, and Acremonium furatum CBS 299.70H.Cellulolytic enzymes may also be obtained from Chrysosporium, preferablya strain of Chrysosporium lucknowense. Additional strains that can beused include, but are not limited to, Trichoderma (particularly T.viride, T. reesei, and T. koningii), alkalophilic Bacillus (see, forexample, U.S. Pat. No. 3,844,890 and EP Pub. No. 0 458 162), andStreptomyces (see, e.g., EP Pub. No. 0 458 162).

In addition to or in combination to enzymes, acids, bases and otherchemicals (e.g., oxidants) can be utilized to saccharify lignocellulosicand cellulosic materials. These can be used in any combination orsequence (e.g., before, after and/or during addition of an enzyme). Forexample, strong mineral acids can be utilized (e.g. HCl, H₂SO₄, H₃PO₄)and strong bases (e.g., NaOH, KOH).

Sugars

In the processes described herein, for example, after saccharification,sugars (e.g., glucose and xylose) can be isolated. For example, sugarscan be isolated by precipitation, crystallization, chromatography (e.g.,simulated moving bed chromatography, high pressure chromatography),centrifugation, extraction, any other isolation method known in the art,and combinations thereof.

Hydrogenation and Other Chemical Transformations

The processes described herein can include hydrogenation. For example,glucose and xylose can be hydrogenated to sorbitol and xylitol,respectively. Hydrogenation can be accomplished by use of a catalyst(e.g., Pt/gamma-Al₂O₃, Ru/C, Raney Nickel, or other catalysts known inthe art) in combination with H₂ under high pressure (e.g., 10 to 12000psi). Other types of chemical transformation of the products from theprocesses described herein can be used, for example, production oforganic sugar derived products (e.g., furfural and furfural-derivedproducts). Chemical transformations of sugar derived products aredescribed in U.S. Ser. No. 13/934,704 filed Jul. 3, 2013, the entiredisclosure of which is incorporated herein by reference.

Fermentation

Yeast and Zymomonas bacteria, for example, can be used for fermentationor conversion of sugar(s) to alcohol(s). Other microorganisms arediscussed below. The optimum pH for fermentations is about pH 4 to 7.For example, the optimum pH for yeast is from about pH 4 to 5, while theoptimum pH for Zymomonas is from about pH 5 to 6. Typical fermentationtimes are about 24 to 168 hours (e.g., 24 to 96 hrs) with temperaturesin the range of 20° C. to 40° C. (e.g., 26° C. to 40° C.); howeverthermophilic microorganisms prefer higher temperatures.

In some embodiments, e.g., when anaerobic organisms are used, at least aportion of the fermentation is conducted in the absence of oxygen, e.g.,under a blanket of an inert gas such as N₂, Ar, He, CO₂ or mixturesthereof. Additionally, the mixture may have a constant purge of an inertgas flowing through the tank during part of or all of the fermentation.In some cases, anaerobic conditions can be achieved or maintained bycarbon dioxide production during the fermentation and no additionalinert gas is needed.

In some embodiments, all or a portion of the fermentation process can beinterrupted before the low molecular weight sugar is completelyconverted to a product (e.g., ethanol). The intermediate fermentationproducts include sugar and carbohydrates in high concentrations. Thesugars and carbohydrates can be isolated via any means known in the art.These intermediate fermentation products can be used in preparation offood for human or animal consumption. Additionally or alternatively, theintermediate fermentation products can be ground to a fine particle sizein a stainless-steel laboratory mill to produce a flour-like substance.Jet mixing may be used during fermentation, and in some casessaccharification and fermentation are performed in the same tank.

Nutrients for the microorganisms may be added during saccharificationand/or fermentation, for example, the food-based nutrient packagesdescribed in U.S. Pat. App. Pub. 2012/0052536, filed Jul. 15, 2011, thecomplete disclosure of which is incorporated herein by reference.

“Fermentation” includes the methods and products that are disclosed inapplication Nos. PCT/US2012/71093 published Jun. 27, 2013,PCT/US2012/71907 published Jun. 27, 2012, and PCT/US2012/71083 publishedJun. 27, 2012 the contents of which are incorporated by reference hereinin their entirety.

Mobile fermenters can be utilized, as described in International App.No. PCT/US2007/074028 (which was filed Jul. 20, 2007, was published inEnglish as WO 2008/011598 and designated the United States) and has a USissued U.S. Pat. No. 8,318,453, the contents of which are incorporatedherein in its entirety. Similarly, the saccharification equipment can bemobile. Further, saccharification and/or fermentation may be performedin part or entirely during transit.

Fermentation Agents

The microorganism(s) used in fermentation can be naturally-occurringmicroorganisms and/or engineered microorganisms. For example, themicroorganism can be a bacterium (including, but not limited to, e.g., acellulolytic bacterium), a fungus, (including, but not limited to, e.g.,a yeast), a plant, a protist, e.g., a protozoa or a fungus-like protest(including, but not limited to, e.g., a slime mold), or an alga. Whenthe organisms are compatible, mixtures of organisms can be utilized.

Suitable fermenting microorganisms have the ability to convertcarbohydrates, such as glucose, fructose, xylose, arabinose, mannose,galactose, oligosaccharides or polysaccharides into fermentationproducts. Fermenting microorganisms include strains of the genusSaccharomyces spp. (including, but not limited to, S. cerevisiae(baker's yeast), S. distaticus, S. uvarum), the genus Kluyveromyces,(including, but not limited to, K. marxianus, K. fragilis), the genusCandida (including, but not limited to, C. pseudotropicalis, and C.brassicae), Pichia stipitis (a relative of Candida shehatae), the genusClavispora (including, but not limited to, C. lusitaniae and C.opuntiae), the genus Pachysolen (including, but not limited to, P.tannophilus), the genus Bretannomyces (including, but not limited to,e.g., B. clausenii (Philippidis, G. P., 1996, Cellulose BioconversionTechnology, in Handbook on Bioethanol: Production and Utilization,Wyman, C. E., ed., Taylor & Francis, Washington, D.C., 179-212)). Othersuitable microorganisms include, for example, Zymomonas mobilis,Clostridium spp. (including, but not limited to, C. thermocellum(Philippidis, 1996, supra), C. saccharobutylacetonicum, C. tyrobutyricumC. saccharobutylicum, C. Puniceum, C. beijernckii, and C.acetobutylicum), Moniliella spp. (including but not limited to M.pollinis, M. tomentosa, M. madida, M. nigrescens, M. oedocephali, M.megachiliensis), Yarrowia lipolytica, Aureobasidium sp.,Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp.,Moniliellaacetoabutans sp., Typhula variabilis, Candida magnoliae,Ustilaginomycetes sp., Pseudozyma tsukubaensis, yeast species of generaZygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fungi of thedematioid genus Torula (e.g., T. corallina).

Additional microorganisms include the Lactobacillus group. Examplesinclude Lactobacillus casei, Lactobacillus rhamnosus, Lactobacillusdelbrueckii, Lactobacillus plantarum, Lactobacillus coryniformis, e.g.,Lactobacillus coryniformis subspecies torquens, Lactobacillus pentosus,Lactobacillus brevis. Other microorganisms include Pediococuspenosaceus, Rhizopus oryzae.

Several organisms, such as bacteria, yeasts and fungi, can be utilizedto ferment biomass derived products such as sugars and alcohols tosuccinic acid and similar products. For example, organisms can beselected from; Actinobacillus succinogenes, Anaerobiospirillumsucciniciproducens, Mannheimia succiniciproducens, Ruminococcusflaverfaciens, Ruminococcus albus, Fibrobacter succinogenes, Bacteroidesfragilis, Bacteroides ruminicola, Bacteroides amylophilus, Bacteroidessuccinogenes, Mannheimia succiniciproducens, Corynebacterium glutamicum,Aspergillus niger, Aspergillus fumigatus, Byssochlamys nivea, Lentinusdegener, Paecilomyces varioti, Penicillium viniferum, Saccharomycescerevisiae, Enterococcus faecali, Prevotella ruminicolas, Debaryomyceshansenii, Candida catenulata VKM Y-5, C. mycoderma VKM Y-240, C. rugosaVKM Y-67, C. paludigena VKM Y-2443, C. utilis VKM Y-74, C. utilis 766,C. zeylanoides VKM Y-6, C. zeylanoides VKM Y-14, C. zeylanoides VKMY-2324, C. zeylanoides VKM Y-1543, C. zeylanoides VKM Y-2595, C. validaVKM Y-934, Kluyveromyces wickerhamii VKM Y-589, Pichia anomala VKMY-118, P. besseyi VKM Y-2084, P. media VKM Y-1381, P. guilliermondiiH-P-4, P. guilliermondii 916, P. inositovora VKM Y-2494, Saccharomycescerevisiae VKM Y-381, Torulopsis candida 127, T. candida 420, Yarrowialipolytica 12a, Y. lipolytica VKM Y-47, Y. lipolytica 69, Y. lipolyticaVKM Y-57, Y. lipolytica 212, Y. lipolytica 374/4, Y. lipolytica 585, Y.lipolytica 695, Y. lipolytica 704, and mixtures of these organisms.

Many such microbial strains are publicly available, either commerciallyor through depositories such as the ATCC (American Type CultureCollection, Manassas, Va., USA), the NRRL (Agricultural Research ServiceCulture Collection, Peoria, Ill., USA), or the DSMZ (Deutsche Sammlungvon Mikroorganismen and Zellkulturen GmbH, Braunschweig, Germany), toname a few.

Commercially available yeasts include, for example, RED STAR®/LesaffreEthanol Red (available from Red Star/Lesaffre, USA), FALI® (availablefrom Fleischmann's Yeast, a division of Burns Philip Food Inc., USA),SUPERSTART® (available from Alltech, now Lalemand), GERT STRAND®(available from Gert Strand AB, Sweden) and FERMOL® (available from DSMSpecialties).

Distillation

After fermentation, the resulting fluids can be distilled using, forexample, a “beer column” to separate ethanol and other alcohols from themajority of water and residual solids. The vapor exiting the beer columncan be, e.g., 35% by weight ethanol and can be fed to a rectificationcolumn. A mixture of nearly azeotropic (92.5%) ethanol and water fromthe rectification column can be purified to pure (99.5%) ethanol usingvapor-phase molecular sieves. The beer column bottoms can be sent to thefirst effect of a three-effect evaporator. The rectification columnreflux condenser can provide heat for this first effect. After the firsteffect, solids can be separated using a centrifuge and dried in a rotarydryer. A portion (25%) of the centrifuge effluent can be recycled tofermentation and the rest sent to the second and third evaporatoreffects. Most of the evaporator condensate can be returned to theprocess as fairly clean condensate with a small portion split off towaste water treatment to prevent build-up of low-boiling compounds.

Hydrocarbon-Containing Materials

In other embodiments utilizing the methods and systems described herein,hydrocarbon-containing materials can be processed. Any process describedherein can be used to treat any hydrocarbon-containing material hereindescribed. “Hydrocarbon-containing materials,” as used herein, is meantto include oil sands, oil shale, tar sands, coal dust, coal slurry,bitumen, various types of coal, and other naturally-occurring andsynthetic materials that include both hydrocarbon components and solidmatter. The solid matter can include wood, rock, sand, clay, stone,silt, drilling slurry, or other solid organic and/or inorganic matter.The term can also include waste products such as drilling waste andby-products, refining waste and by-products, or other waste productscontaining hydrocarbon components, such as asphalt shingling andcovering, asphalt pavement, etc.

In yet other embodiments utilizing the methods and systems describedherein, wood and wood containing produces can be processed. For examplelumber products can be processed, e.g. boards, sheets, laminates, beams,particle boards, composites, rough cut wood, soft wood and hard wood. Inaddition cut trees, bushes, wood chips, saw dust, roots, bark, stumps,decomposed wood and other wood containing biomass material can beprocessed.

Conveying Systems

Various conveying systems can be used to convey the biomass material,for example, as discussed, to a vault, and under an electron beam in avault. Exemplary conveyors are belt conveyors, pneumatic conveyors,screw conveyors, carts, trains, trains or carts on rails, elevators,front loaders, backhoes, cranes, various scrapers and shovels, trucks,and throwing devices can be used. For example, vibratory conveyors canbe used in various processes described herein. Vibratory conveyors aredescribed in PCT/US2013/64289 filed Oct. 10, 2013 the full disclosure ofwhich is incorporated by reference herein.

Vibratory conveyors are particularly useful for spreading the materialand producing a uniform layer on the conveyor trough surface. Forexample the initial feedstock can form a pile of material that can be atleast four feet high (e.g., at least about 3 feet, at least about 2feet, at least about 1 foot, at least about 6 inches, at least about 5inches, at least about, 4 inches, at least about 3 inches, at leastabout 2 inches, at least about 1 inch, at least about ½ inch) and spansless than the width of the conveyor (e.g., less than about 10%, lessthan about 20%, less than about 30%, less than about 40%, less thanabout 50%, less than about 60%, less than about 70%, less than about80%, less than about 90%, less than about 95%, less than about 99%). Thevibratory conveyor can spread the material to span the entire width ofthe conveyor trough and have a uniform thickness, preferably asdiscussed above. In some cases, an additional spreading method can beuseful. For example, a spreader such as a broadcast spreader, a dropspreader (e.g., a CHRISTY SPREADER™) or combinations thereof can be usedto drop (e.g., place, pour, spill and/or sprinkle) the feedstock over awide area. Optionally, the spreader can deliver the biomass as a wideshower or curtain onto the vibratory conveyor. Additionally, a secondconveyor, upstream from the first conveyor (e.g., the first conveyor isused in the irradiation of the feedstock), can drop biomass onto thefirst conveyor, where the second conveyor can have a width transverse tothe direction of conveying smaller than the first conveyor. Inparticular, when the second conveyor is a vibratory conveyor, thefeedstock is spread by the action of the second and first conveyor. Insome optional embodiments, the second conveyor ends in a bias cross cutdischarge (e.g., a bias cut with a ratio of 4:1) so that the materialcan be dropped as a wide curtain (e.g., wider than the width of thesecond conveyor) onto the first conveyor. The initial drop area of thebiomass by the spreader (e.g., broadcast spreader, drop spreader,conveyor, or cross cut vibratory conveyor) can span the entire width ofthe first vibratory conveyor, or it can span part of this width. Oncedropped onto the conveyor, the material is spread even more uniformly bythe vibrations of the conveyor so that, preferably, the entire width ofthe conveyor is covered with a uniform layer of biomass. In someembodiments combinations of spreaders can be used. Some methods ofspreading a feed stock are described in U.S. Pat. No. 7,153,533, filedJul. 23, 2002 and published Dec. 26, 2006, the entire disclosure ofwhich is incorporated herein by reference.

Generally, it is preferred to convey the material as quickly as possiblethrough an electron beam to maximize throughput. For example, thematerial can be conveyed at rates of at least 1 ft/min, e.g., at least 2ft/min, at least 3 ft/min, at least 4 ft/min, at least 5 ft/min, atleast 10 ft/min, at least 15 ft/min, at least 20 ft/min, at least 25ft/min, at least 30 ft/min, at least 40 ft/min, at least 50 ft/min, atleast 60 ft/min, at least 70 ft/min, at least 80 ft/min, at least 90ft/min. The rate of conveying is related to the beam current andtargeted irradiation dose, for example, for a ¼ inch thick biomassspread over a 5.5 foot wide conveyor and 100 mA, the conveyor can moveat about 20 ft/min to provide a useful irradiation dosage (e.g. about 10Mrad for a single pass), at 50 mA the conveyor can move at about 10ft/min to provide approximately the same irradiation dosage.

The rate at which material can be conveyed depends on the shape and massof the material being conveyed and the desired treatment. Flowingmaterials e.g., particulate materials, are particularly amenable toconveying with vibratory conveyors. Conveying speeds can, for examplebe, at least 100 lb/hr (e.g., at least 500 lb/hr, at least 1000 lb/hr,at least 2000 lb/hr, at least 3000 lb/hr, at least 4000 lb/hr, at least5000 lb/hr, at least 10,000 lb/hr, at least 15,000 lb/hr, or even atleast 25,000 lb/hr). Some typical conveying speeds can be between about1000 and 10,000 lb/hr, (e.g., between about 1000 lb/hr and 8000 lb/hr,between about 2000 and 7000 lb/hr, between about 2000 and 6000 lb/hr,between about 2000 and 5000 lb/hr, between about 2000 and 4500 lb/hr,between about 1500 and 5000 lb/hr, between about 3000 and 7000 lb/hr,between about 3000 and 6000 lb/hr, between about 4000 and 6000 lb/hr andbetween about 4000 and 5000 lb/hr). Typical conveying speeds depend onthe density of the material. For example, for a biomass with a densityof about 35 lb/ft3, and a conveying speed of about 5000 lb/hr, thematerial is conveyed at a rate of about 143 ft3/hr, if the material is¼″ thick and is in a trough 5.5 ft wide, the material is conveyed at arate of about 1250 ft/hr (about 21 ft/min). Rates of conveying thematerial can therefore vary greatly. Preferably, for example, a ¼″ thicklayer of biomass, is conveyed at speeds of between about 5 and 100ft/min (e.g. between about 5 and 100 ft/min, between about 6 and 100ft/min, between about 7 and 100 ft/min, between about 8 and 100 ft/min,between about 9 and 100 ft/min, between about 10 and 100 ft/min, betweenabout 11 and 100 ft/min, between about 12 and 100 ft/min, between about13 and 100 ft/min, between about 14 and 100 ft/min, between about 15 and100 ft/min, between about 20 and 100 ft/min, between about 30 and 100ft/min, between about 40 and 100 ft/min, between about 2 and 60 ft/min,between about 3 and 60 ft/min, between about 5 and 60 ft/min, betweenabout 6 and 60 ft/min, between about 7 and 60 ft/min, between about 8and 60 ft/min, between about 9 and 60 ft/min, between about 10 and 60ft/min, between about 15 and 60 ft/min, between about 20 and 60 ft/min,between about 30 and 60 ft/min, between about 40 and 60 ft/min, betweenabout 2 and 50 ft/min, between about 3 and 50 ft/min, between about 5and 50 ft/min, between about 6 and 50 ft/min, between about 7 and 50ft/min, between about 8 and 50 ft/min, between about 9 and 50 ft/min,between about 10 and 50 ft/min, between about 15 and 50 ft/min, betweenabout 20 and 50 ft/min, between about 30 and 50 ft/min, between about 40and 50 ft/min). It is preferable that the material be conveyed at aconstant rate, for example, to help maintain a constant irradiation ofthe material as it passes under the electron beam (e.g., shower, field).

The vibratory conveyors described can include screens used for sievingand sorting materials. Port openings on the side or bottom of thetroughs can be used for sorting, selecting or removing specificmaterials, for example, by size or shape. Some conveyors havecounterbalances to reduce the dynamic forces on the support structure.Some vibratory conveyors are configured as spiral elevators, aredesigned to curve around surfaces and/or are designed to drop materialfrom one conveyor to another (e.g., in a step, cascade or as a series ofsteps or a stair). Along with conveying materials conveyors can be used,by themselves or coupled with other equipment or systems, for screening,separating, sorting, classifying, distributing, sizing, inspection,picking, metal removing, freezing, blending, mixing, orienting, heating,cooking, drying, dewatering, cleaning, washing, leaching, quenching,coating, de-dusting and/or feeding. The conveyors can also includecovers (e.g., dust-tight covers), side discharge gates, bottom dischargegates, special liners (e.g., anti-stick, stainless steel, rubber, customsteal, and or grooved), divided troughs, quench pools, screens,perforated plates, detectors (e.g., metal detectors), high temperaturedesigns, food grade designs, heaters, dryers and or coolers. Inaddition, the trough can be of various shapes, for example, flatbottomed, vee shaped bottom, flanged at the top, curved bottom, flatwith ridges in any direction, tubular, half pipe, covered or anycombinations of these. In particular, the conveyors can be coupled withan irradiation systems and/or equipment.

The conveyors (e.g., vibratory conveyor) can be made of corrosionresistant materials. The conveyors can utilize structural materials thatinclude stainless steel (e.g., 304, 316 stainless steel, HASTELLOY®ALLOYS and INCONEL® Alloys). For example, HASTELLOY® Corrosion-Resistantalloys from Hynes (Kokomo, Ind., USA) such as HASTELLOY® B-3® ALLOY,HASTELLOY® HYBRID-BC1® ALLOY, HASTELLOY® C-4 ALLOY, HASTELLOY® C-22®ALLOY, HASTELLOY® C-22HS® ALLOY, HASTELLOY® C-276 ALLOY, HASTELLOY®C-2000® ALLOY, HASTELLOY® G-30® ALLOY, HASTELLOY® G-35® ALLOY,HASTELLOY® N ALLOY and HASTELLOY® ULTIMET® alloy.

The vibratory conveyors can include non-stick release coatings, forexample, TUFFLON™ (Dupont, Del., USA). The vibratory conveyors can alsoinclude corrosion resistant coatings. For example, coatings that can besupplied from Metal Coatings Corp (Houston, Tex., USA) and others suchas Fluoropolymer, XYLAN®, Molybdenum Disulfide, Epoxy Phenolic,Phosphate-ferrous metal coating, Polyurethane-high gloss topcoat forepoxy, inorganic zinc, Poly Tetrafluoro ethylene, PPS/RYTON®,fluorinated ethylene propylene, PVDF/DYKOR®, ECTFE/HALAR® and CeramicEpoxy Coating. The coatings can improve resistance to process gases(e.g., ozone), chemical corrosion, pitting corrosion, galling corrosionand oxidation.

Optionally, in addition to the conveying systems described herein, oneor more other conveying systems can be enclosed. When using anenclosure, the enclosed conveyor can also be purged with an inert gas soas to maintain an atmosphere at a reduced oxygen level. Keeping oxygenlevels low avoids the formation of ozone which in some instances isundesirable due to its reactive and toxic nature. For example, theoxygen can be less than about 20% (e.g., less than about 10%, less thanabout 1%, less than about 0.1%, less than about 0.01%, or even less thanabout 0.001% oxygen). Purging can be done with an inert gas including,but not limited to, nitrogen, argon, helium or carbon dioxide. This canbe supplied, for example, from a boil off of a liquid source (e.g.,liquid nitrogen or helium), generated or separated from air in situ, orsupplied from tanks. The inert gas can be recirculated and any residualoxygen can be removed using a catalyst, such as a copper catalyst bed.Alternatively, combinations of purging, recirculating and oxygen removalcan be done to keep the oxygen levels low.

The enclosed conveyor can also be purged with a reactive gas that canreact with the biomass. This can be done before, during or after theirradiation process. The reactive gas can be, but is not limited to,nitrous oxide, ammonia, oxygen, ozone, hydrocarbons, aromatic compounds,amides, peroxides, azides, halides, oxyhalides, phosphides, phosphines,arsines, sulfides, thiols, boranes and/or hydrides. The reactive gas canbe activated in the enclosure, e.g., by irradiation (e.g., electronbeam, UV irradiation, microwave irradiation, heating, IR radiation), sothat it reacts with the biomass. The biomass itself can be activated,for example by irradiation. Preferably the biomass is activated by theelectron beam, to produce radicals which then react with the activatedor unactivated reactive gas, e.g., by radical coupling or quenching.

Purging gases supplied to an enclosed conveyor can also be cooled, forexample below about 25° C., below about 0° C., below about −40° C.,below about −80° C., below about −120° C. For example, the gas can beboiled off from a compressed gas such as liquid nitrogen or sublimedfrom solid carbon dioxide. As an alternative example, the gas can becooled by a chiller or part of or the entire conveyor can be cooled.

Other Embodiments

Any material, processes or processed materials discussed herein can beused to make products and/or intermediates such as composites, fillers,binders, plastic additives, adsorbents and controlled release agents.The methods can include densification, for example, by applying pressureand heat to the materials. For example composites can be made bycombining fibrous materials with a resin or polymer. For exampleradiation cross-linkable resin, e.g., a thermoplastic resin can becombined with a fibrous material to provide a fibrousmaterial/cross-linkable resin combination. Such materials can be, forexample, useful as building materials, protective sheets, containers andother structural materials (e.g., molded and/or extruded products).Absorbents can be, for example, in the form of pellets, chips, fibersand/or sheets. Adsorbents can be used, for example, as pet bedding,packaging material or in pollution control systems. Controlled releasematrices can also be the form of, for example, pellets, chips, fibersand or sheets. The controlled release matrices can, for example, be usedto release drugs, biocides, fragrances. For example, composites,absorbents and control release agents and their uses are described inInternational Serial No. PCT/US2006/010648, filed Mar. 23, 2006, andU.S. Pat. No. 8,074,910 filed Nov. 22, 2011, the entire disclosures ofwhich are herein incorporated by reference.

In some instances the biomass material is treated at a first level toreduce recalcitrance, e.g., utilizing accelerated electrons, toselectively release one or more sugars (e.g., xylose). The biomass canthen be treated to a second level to release one or more other sugars(e.g., glucose). Optionally the biomass can be dried between treatments.The treatments can include applying chemical and biochemical treatmentsto release the sugars. For example, a biomass material can be treated toa level of less than about 20 Mrad (e.g., less than about 15 Mrad, lessthan about 10 Mrad, less than about 5 Mrad, less than about 2 Mrad) andthen treated with a solution of sulfuric acid, containing less than 10%sulfuric acid (e.g., less than about 9%, less than about 8%, less thanabout 7%, less than about 6%, less than about 5%, less than about 4%,less than about 3%, less than about 2%, less than about 1%, less thanabout 0.75%, less than about 0.50%, less than about 0.25%) to releasexylose. Xylose, for example that is released into solution, can beseparated from solids and optionally the solids washed with asolvent/solution (e.g., with water and/or acidified water). Optionally,the Solids can be dried, for example in air and/or under vacuumoptionally with heating (e.g., below about 150 deg C., below about 120deg C.) to a water content below about 25 wt. % (below about 20 wt. %,below about 15 wt. %, below about 10 wt. %, below about 5 wt. %). Thesolids can then be treated with a level of less than about 30 Mrad(e.g., less than about 25 Mrad, less than about 20 Mrad, less than about15 Mrad, less than about 10 Mrad, less than about 5 Mrad, less thanabout 1 Mrad or even not at all) and then treated with an enzyme (e.g.,a cellulase) to release glucose. The glucose (e.g., glucose in solution)can be separated from the remaining solids. The solids can then befurther processed, for example utilized to make energy or other products(e.g., lignin derived products).

Flavors, Fragrances and Colorants

Any of the products and/or intermediates described herein, for example,produced by the processes, systems and/or equipment described herein,can be combined with flavors, fragrances, colorants and/or mixtures ofthese. For example, any one or more of (optionally along with flavors,fragrances and/or colorants) sugars, organic acids, fuels, polyols, suchas sugar alcohols, biomass, fibers and composites can be combined with(e.g., formulated, mixed or reacted) or used to make other products. Forexample, one or more such product can be used to make soaps, detergents,candies, drinks (e.g., cola, wine, beer, liquors such as gin or vodka,sports drinks, coffees, teas), syrups, pharmaceuticals, adhesives,sheets (e.g., woven, none woven, filters, tissues) and/or composites(e.g., boards). For example, one or more such product can be combinedwith herbs, flowers, petals, spices, vitamins, potpourri, or candles.For example, the formulated, mixed or reacted combinations can haveflavors/fragrances of grapefruit, orange, apple, raspberry, banana,lettuce, celery, cinnamon, chocolate, vanilla, peppermint, mint, onion,garlic, pepper, saffron, ginger, milk, wine, beer, tea, lean beef, fish,clams, olive oil, coconut fat, pork fat, butter fat, beef bouillon,legume, potatoes, marmalade, ham, coffee and cheeses.

Flavors, fragrances and colorants can be added in any amount, such asbetween about 0.001 wt. % to about 30 wt. %, e.g., between about 0.01 toabout 20, between about 0.05 to about 10, or between about 0.1 wt. % toabout 5 wt. %. These can be formulated, mixed and or reacted (e.g., withany one of more product or intermediate described herein) by any meansand in any order or sequence (e.g., agitated, mixed, emulsified, gelled,infused, heated, sonicated, and/or suspended). Fillers, binders,emulsifier, antioxidants can also be utilized, for example protein gels,starches and silica.

In one embodiment the flavors, fragrances and colorants can be added tothe biomass immediately after the biomass is irradiated such that thereactive sites created by the irradiation may react with reactivecompatible sites of the flavors, fragrances, and colorants.

The flavors, fragrances and colorants can be natural and/or syntheticmaterials. These materials can be one or more of a compound, acomposition or mixtures of these (e.g., a formulated or naturalcomposition of several compounds). Optionally the flavors, fragrances,antioxidants and colorants can be derived biologically, for example,from a fermentation process (e.g., fermentation of saccharifiedmaterials as described herein). Alternatively, or additionally theseflavors, fragrances and colorants can be harvested from a whole organism(e.g., plant, fungus, animal, bacteria or yeast) or a part of anorganism. The organism can be collected and or extracted to providecolor, flavors, fragrances and/or antioxidant by any means includingutilizing the methods, systems and equipment described herein, hot waterextraction, supercritical fluid extraction, chemical extraction (e.g.,solvent or reactive extraction including acids and bases), mechanicalextraction (e.g., pressing, comminuting, filtering), utilizing anenzyme, utilizing a bacteria such as to break down a starting material,and combinations of these methods. The compounds can be derived by achemical reaction, for example, the combination of a sugar (e.g., asproduced as described herein) with an amino acid (Maillard reaction).The flavor, fragrance, antioxidant and/or colorant can be anintermediate and or product produced by the methods, equipment orsystems described herein, for example and ester and a lignin derivedproduct.

Some examples of flavor, fragrances or colorants are polyphenols.Polyphenols are pigments responsible for the red, purple and bluecolorants of many fruits, vegetables, cereal grains, and flowers.Polyphenols also can have antioxidant properties and often have a bittertaste. The antioxidant properties make these important preservatives. Onclass of polyphenols are the flavonoids, such as Anthocyanidines,flavanonols, flavan-3-ols, s, flavanones and flavanonols. Other phenoliccompounds that can be used include phenolic acids and their esters, suchas chlorogenic acid and polymeric tannins.

Among the colorants inorganic compounds, minerals or organic compoundscan be used, for example titanium dioxide, zinc oxide, aluminum oxide,cadmium yellow (E.g., CdS), cadmium orange (e.g., CdS with some Se),alizarin crimson (e.g., synthetic or non-synthetic rose madder),ultramarine (e.g., synthetic ultramarine, natural ultramarine, syntheticultramarine violet), cobalt blue, cobalt yellow, cobalt green, viridian(e.g., hydrated chromium(III)oxide), chalcophylite, conichalcite,cornubite, cornwallite and liroconite. Black pigments such as carbonblack and self-dispersed blacks may be used.

Some flavors and fragrances that can be utilized include ACALEA TBHQ,ACET C-6, ALLYL AMYL GLYCOLATE, ALPHA TERPINEOL, AMBRETTOLIDE, AMBRINOL95, ANDRANE, APHERMATE, APPLELIDE, BACDANOL®, BERGAMAL, BETA IONONEEPDXIDE, BETA NAPHTHYL ISO-BUTYL ETHER, BICYCLONONALACTONE, BORNAFIX®,CANTHOXAL, CASHMERAN®, CASHMERAN® VELVET, CASSIFFIX®, CEDRAFIX,CEDRAMBER®, CEDRYL ACETATE, CELESTOLIDE, CINNAMALVA, CITRAL DIMETHYLACETATE, CITROLATE™, CITRONELLOL 700, CITRONELLOL 950, CITRONELLOLCOEUR, CITRONELLYL ACETATE, CITRONELLYL ACETATE PURE, CITRONELLYLFORMATE, CLARYCET, CLONAL, CONIFERAN, CONIFERAN PURE, CORTEX ALDEHYDE50% PEOMOSA, CYCLABUTE, CYCLACET®, CYCLAPROP®, CYCLEMAX™, CYCLOHEXYLETHYL ACETATE, DAMASCOL, DELTA DAMASCONE, DIHYDRO CYCLACET, DIHYDROMYRCENOL, DIHYDRO TERPINEOL, DIHYDRO TERPINYL ACETATE, DIMETHYLCYCLORMOL, DIMETHYL OCTANOL PQ, DIMYRCETOL, DIOLA, DIPENTENE, DULCINYL®RECRYSTALLIZED, ETHYL-3-PHENYL GLYCIDATE, FLEURAMONE, FLEURANIL, FLORALSUPER, FLORALOZONE, FLORIFFOL, FRAISTONE, FRUCTONE, GALAXOLIDE® 50,GALAXOLIDE® 50 BB, GALAXOLIDE® 50 IPM, GALAXOLIDE® UNDILUTED,GALBASCONE, GERALDEHYDE, GERANIOL 5020, GERANIOL 600 TYPE, GERANIOL 950,GERANIOL 980 (PURE), GERANIOL CFT COEUR, GERANIOL COEUR, GERANYL ACETATECOEUR, GERANYL ACETATE, PURE, GERANYL FORMATE, GRISALVA, GUAIYL ACETATE,HELIONAL™, HERBAC, HERBALIME™, HEXADECANOLIDE, HEXALON, HEXENYLSALICYLATE CIS 3-, HYACINTH BODY, HYACINTH BODY NO. 3, HYDRATROPICALDEHYDE.DMA, HYDROXYOL, INDOLAROME, INTRELEVEN ALDEHYDE, INTRELEVENALDEHYDE SPECIAL, IONONE ALPHA, IONONE BETA, ISO CYCLO CITRAL, ISO CYCLOGERANIOL, ISO E SUPER®, ISOBUTYL QUINOLINE, JASMAL, JESSEMAL®,KHARISMAL®, KHARISMAL® SUPER, KHUSINIL, KOAVONE®, KOHINOOL®, LIFFAROME™,LIMOXAL, LINDENOL™, LYRAL®, LYRAME SUPER, MANDARIN ALD 10% TRI ETH,CITR, MARITIMA, MCK CHINESE, MEIJIFF™, MELAFLEUR, MELOZONE, METHYLANTHRANILATE, METHYL IONONE ALPHA EXTRA, METHYL IONONE GAMMA A, METHYLIONONE GAMMA COEUR, METHYL IONONE GAMMA PURE, METHYL LAVENDER KETONE,MONTAVERDI®, MUGUESIA, MUGUET ALDEHYDE 50, MUSK Z4, MYRAC ALDEHYDE,MYRCENYL ACETATE, NECTARATE™, NEROL 900, NERYL ACETATE, OCIMENE,OCTACETAL, ORANGE FLOWER ETHER, ORIVONE, ORRINIFF 25%, OXASPIRANE,OZOFLEUR, PAMPLEFLEUR®, PEOMOSA, PHENOXANOL®, PICONIA, PRECYCLEMONE B,PRENYL ACETATE, PRISMANTOL, RESEDA BODY, ROSALVA, ROSAMUSK, SANJINOL,SANTALIFF™, SYVERTAL, TERPINEOL, TERPINOLENE 20, TERPINOLENE 90 PQ,TERPINOLENE RECT., TERPINYL ACETATE, TERPINYL ACETATE JAX, TETRAHYDRO,MUGUOL®, TETRAHYDRO MYRCENOL, TETRAMERAN, TIMBERSILK™, TOBACAROL,TRIMOFIX® 0 TT, TRIPLAL®, TRIS AMBER®, VANORIS, VERDOX™, VERDOX™ HC,VERTENEX®, VERTENEX® HC, VERTOFIX® COEUR, VERTOLIFF, VERTOLIFF ISO,VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75 PCT MIGLYOL, ABS MOROCCO 50PCT DPG, ABS MOROCCO 50 PCT TEC, ABSOLUTE FRENCH, ABSOLUTE INDIA,ABSOLUTE MD 50 PCT BB, ABSOLUTE MOROCCO, CONCENTRATE PG, TINCTURE 20PCT, AMBERGRIS, AMBRETTE ABSOLUTE, AMBRETTE SEED OIL, ARMOISE OIL 70 PCTTHUYONE, BASIL ABSOLUTE GRAND VERT, BASIL GRAND VERT ABS MD, BASIL OILGRAND VERT, BASIL OIL VERVEINA, BASIL OIL VIETNAM, BAY OIL TERPENELESS,BEESWAX ABS N G, BEESWAX ABSOLUTE, BENZOIN RESINOID SIAM, BENZOINRESINOID SIAM 50 PCT DPG, BENZOIN RESINOID SIAM 50 PCT PG, BENZOINRESINOID SIAM 70.5 PCT TEC, BLACKCURRANT BUD ABS 65 PCT PG, BLACKCURRANTBUD ABS MD 37 PCT TEC, BLACKCURRANT BUD ABS MIGLYOL, BLACKCURRANT BUDABSOLUTE BURGUNDY, BOIS DE ROSE OIL, BRAN ABSOLUTE, BRAN RESINOID, BROOMABSOLUTE ITALY, CARDAMOM GUATEMALA CO2 EXTRACT, CARDAMOM OIL GUATEMALA,CARDAMOM OIL INDIA, CARROT HEART, CASSIE ABSOLUTE EGYPT, CASSIE ABSOLUTEMD 50 PCT IPM, CASTOREUM ABS 90 PCT TEC, CASTOREUM ABS C 50 PCT MIGLYOL,CASTOREUM ABSOLUTE, CASTOREUM RESINOID, CASTOREUM RESINOID 50 PCT DPG,CEDROL CEDRENE, CEDRUS ATLANTICA OIL REDIST, CHAMOMILE OIL ROMAN,CHAMOMILE OIL WILD, CHAMOMILE OIL WILD LOW LIMONENE, CINNAMON BARK OILCEYLAN, CISTE ABSOLUTE, CISTE ABSOLUTE COLORLESS, CITRONELLA OIL ASIAIRON FREE, CIVET ABS 75 PCT PG, CIVET ABSOLUTE, CIVET TINCTURE 10 PCT,CLARY SAGE ABS FRENCH DECOL, CLARY SAGE ABSOLUTE FRENCH, CLARY SAGEC'LESS 50 PCT PG, CLARY SAGE OIL FRENCH, COPAIBA BALSAM, COPAIBA BALSAMOIL, CORIANDER SEED OIL, CYPRESS OIL, CYPRESS OIL ORGANIC, DAVANA OIL,GALBANOL, GALBANUM ABSOLUTE COLORLESS, GALBANUM OIL, GALBANUM RESINOID,GALBANUM RESINOID 50 PCT DPG, GALBANUM RESINOID HERCOLYN BHT, GALBANUMRESINOID TEC BHT, GENTIANE ABSOLUTE MD 20 PCT BB, GENTIANE CONCRETE,GERANIUM ABS EGYPT MD, GERANIUM ABSOLUTE EGYPT, GERANIUM OIL CHINA,GERANIUM OIL EGYPT, GINGER OIL 624, GINGER OIL RECTIFIED SOLUBLE,GUAIACWOOD HEART, HAY ABS MD 50 PCT BB, HAY ABSOLUTE, HAY ABSOLUTE MD 50PCT TEC, HEALINGWOOD, HYSSOP OIL ORGANIC, IMMORTELLE ABS YUGO MD 50 PCTTEC, IMMORTELLE ABSOLUTE SPAIN, IMMORTELLE ABSOLUTE YUGO, JASMIN ABSINDIA MD, JASMIN ABSOLUTE EGYPT, JASMIN ABSOLUTE INDIA, ASMIN ABSOLUTEMOROCCO, JASMIN ABSOLUTE SAMBAC, JONQUILLE ABS MD 20 PCT BB, JONQUILLEABSOLUTE France, JUNIPER BERRY OIL FLG, JUNIPER BERRY OIL RECTIFIEDSOLUBLE, LABDANUM RESINOID 50 PCT TEC, LABDANUM RESINOID BB, LABDANUMRESINOID MD, LABDANUM RESINOID MD 50 PCT BB, LAVANDIN ABSOLUTE H,LAVANDIN ABSOLUTE MD, LAVANDIN OIL ABRIAL ORGANIC, LAVANDIN OIL GROSSOORGANIC, LAVANDIN OIL SUPER, LAVENDER ABSOLUTE H, LAVENDER ABSOLUTE MD,LAVENDER OIL COUMARIN FREE, LAVENDER OIL COUMARIN FREE ORGANIC, LAVENDEROIL MAILLETTE ORGANIC, LAVENDER OIL MT, MACE ABSOLUTE BB, MAGNOLIAFLOWER OIL LOW METHYL EUGENOL, MAGNOLIA FLOWER OIL, MAGNOLIA FLOWER OILMD, MAGNOLIA LEAF OIL, MANDARIN OIL MD, MANDARIN OIL MD BHT, MATEABSOLUTE BB, MOSS TREE ABSOLUTE MD TEX IFRA 43, MOSS-OAK ABS MD TEC IFRA43, MOSS-OAK ABSOLUTE IFRA 43, MOSS-TREE ABSOLUTE MD IPM IFRA 43, MYRRHRESINOID BB, MYRRH RESINOID MD, MYRRH RESINOID TEC, MYRTLE OIL IRONFREE, MYRTLE OIL TUNISIA RECTIFIED, NARCISSE ABS MD 20 PCT BB, NARCISSEABSOLUTE FRENCH, NEROLI OIL TUNISIA, NUTMEG OIL TERPENELESS, OEILLETABSOLUTE, OLIBANUM RESINOID, OLIBANUM RESINOID BB, OLIBANUM RESINOIDDPG, OLIBANUM RESINOID EXTRA 50 PCT DPG, OLIBANUM RESINOID MD, OLIBANUMRESINOID MD 50 PCT DPG, OLIBANUM RESINOID TEC, OPOPONAX RESINOID TEC,ORANGE BIGARADE OIL MD BHT, ORANGE BIGARADE OIL MD SCFC, ORANGE FLOWERABSOLUTE TUNISIA, ORANGE FLOWER WATER ABSOLUTE TUNISIA, ORANGE LEAFABSOLUTE, ORANGE LEAF WATER ABSOLUTE TUNISIA, ORRIS ABSOLUTE ITALY,ORRIS CONCRETE 15 PCT IRONE, ORRIS CONCRETE 8 PCT IRONE, ORRIS NATURAL15 PCT IRONE 4095C, ORRIS NATURAL 8 PCT IRONE 2942C, ORRIS RESINOID,OSMANTHUS ABSOLUTE, OSMANTHUS ABSOLUTE MD 50 PCT BB, PATCHOULI HEARTN^(o) 3, PATCHOULI OIL INDONESIA, PATCHOULI OIL INDONESIA IRON FREE,PATCHOULI OIL INDONESIA MD, PATCHOULI OIL REDIST, PENNYROYAL HEART,PEPPERMINT ABSOLUTE MD, PETITGRAIN BIGARADE OIL TUNISIA, PETITGRAINCITRONNIER OIL, PETITGRAIN OIL PARAGUAY TERPENELESS, PETITGRAIN OILTERPENELESS STAB, PIMENTO BERRY OIL, PIMENTO LEAF OIL, RHODINOL EXGERANIUM CHINA, ROSE ABS BULGARIAN LOW METHYL EUGENOL, ROSE ABS MOROCCOLOW METHYL EUGENOL, ROSE ABS TURKISH LOW METHYL EUGENOL, ROSE ABSOLUTE,ROSE ABSOLUTE BULGARIAN, ROSE ABSOLUTE DAMASCENA, ROSE ABSOLUTE MD, ROSEABSOLUTE MOROCCO, ROSE ABSOLUTE TURKISH, ROSE OIL BULGARIAN, ROSE OILDAMASCENA LOW METHYL EUGENOL, ROSE OIL TURKISH, ROSEMARY OIL CAMPHORORGANIC, ROSEMARY OIL TUNISIA, SANDALWOOD OIL INDIA, SANDALWOOD OILINDIA RECTIFIED, SANTALOL, SCHINUS MOLLE OIL, ST JOHN BREAD TINCTURE 10PCT, STYRAX RESINOID, STYRAX RESINOID, TAGETE OIL, TEA TREE HEART, TONKABEAN ABS 50 PCT SOLVENTS, TONKA BEAN ABSOLUTE, TUBEROSE ABSOLUTE INDIA,VETIVER HEART EXTRA, VETIVER OIL HAITI, VETIVER OIL HAITI MD, VETIVEROIL JAVA, VETIVER OIL JAVA MD, VIOLET LEAF ABSOLUTE EGYPT, VIOLET LEAFABSOLUTE EGYPT DECOL, VIOLET LEAF ABSOLUTE FRENCH, VIOLET LEAF ABSOLUTEMD 50 PCT BB, WORMWOOD OIL TERPENELESS, YLANG EXTRA OIL, YLANG III OILand combinations of these.

The colorants can be among those listed in the Color Index Internationalby the Society of Dyers and Colourists. Colorants include dyes andpigments and include those commonly used for coloring textiles, paints,inks and inkjet inks. Some colorants that can be utilized includecarotenoids, arylide yellows, diarylide yellows, β-naphthols, naphthols,benzimidazolones, disazo condensation pigments, pyrazolones, nickel azoyellow, phthalocyanines, quinacridones, perylenes and perinones,isoindolinone and isoindoline pigments, triarylcarbonium pigments,diketopyrrolo-pyrrole pigments, thioindigoids. Cartenoids include, forexample, alpha-carotene, beta-carotene, gamma-carotene, lycopene, luteinand astaxanthin, Annatto extract, Dehydrated beets (beet powder),Canthaxanthin, Caramel, β-Apo-8′-carotenal, Cochineal extract, Carmine,Sodium copper chlorophyllin, Toasted partially defatted cookedcottonseed flour, Ferrous gluconate, Ferrous lactate, Grape colorextract, Grape skin extract (enocianina), Carrot oil, Paprika, Paprikaoleoresin, Mica-based pearlescent pigments, Riboflavin, Saffron,Titanium dioxide, Tomato lycopene extract; tomato lycopene concentrate,Turmeric, Turmeric oleoresin, FD&C Blue No. 1, FD&C Blue No. 2, FD&CGreen No. 3, Orange B, Citrus Red No. 2, FD&C Red No. 3, FD&C Red No.40, FD&C Yellow No. 5, FD&C Yellow No. 6, Alumina (dried aluminumhydroxide), Calcium carbonate, Potassium sodium copper chlorophyllin(chlorophyllin-copper complex), Dihydroxyacetone, Bismuth oxychloride,Ferric ammonium ferrocyanide, Ferric ferrocyanide, Chromium hydroxidegreen, Chromium oxide greens, Guanine, Pyrophyllite, Talc, Aluminumpowder, Bronze powder, Copper powder, Zinc oxide, D&C Blue No. 4, D&CGreen No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&COrange No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C Red No. 4, D&CRed No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C Red No.22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&CRed No. 33, D&C Red No. 34, D&C Red No. 36, D&C Red No. 39, D&C VioletNo. 2, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&CYellow No. 10, D&C Yellow No. 11, D&C Black No. 2, D&C Black No. 3 (3),D&C Brown No. 1, Ext. D&C, Chromium-cobalt-aluminum oxide, Ferricammonium citrate, Pyrogallol, Logwood extract,1,4-Bis[(2-hydroxy-ethyl)amino]-9,10-anthracenedionebis(2-propenoic)ester copolymers, 1,4-Bis[(2-methylphenyl)amino]-9,10-anthracenedione,1,4-Bis[4-(2-methacryloxyethyl) phenylamino] anthraquinone copolymers,Carbazole violet, Chlorophyllin-copper complex, Chromium-cobalt-aluminumoxide, C.I. Vat Orange 1, 2-[[2,5-Diethoxy-4-[(4-methylphenyl)thiol]phenyl]azo]-1,3,5-benzenetriol, 16,23-Dihydrodinaphtho [2,3-a:2′,3′-i]naphth [2′,3′: 6,7] indolo [2,3-c] carbazole-5,10,15,17,22,24-hexone,N,N′-(9,10-Dihydro-9,10-dioxo-1,5-anthracenediyl) bisbenzamide,7,16-Dichloro-6,15-dihydro-5,9,14,18-anthrazinetetrone,16,17-Dimethoxydinaphtho (1,2,3-cd:3′,2′,1′-lm) perylene-5,10-dione,Poly(hydroxyethyl methacrylate)-dye copolymers(3), Reactive Black 5,Reactive Blue 21, Reactive Orange 78, Reactive Yellow 15, Reactive BlueNo. 19, Reactive Blue No. 4, C.I. Reactive Red 11, C.I. Reactive Yellow86, C.I. Reactive Blue 163, C.I. Reactive Red 180,4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one(solvent Yellow 18), 6-Ethoxy-2-(6-ethoxy-3-oxobenzo[b]thien-2(3H)-ylidene) benzo[b]thiophen-3(2H)-one, Phthalocyanine green,Vinyl alcohol/methyl methacrylate-dye reaction products, C.I. ReactiveRed 180, C.I. Reactive Black 5, C.I. Reactive Orange 78, C.I. ReactiveYellow 15, C.I. Reactive Blue 21, Disodium1-amino-4-[[4-[(2-bromo-1-oxoallyl)amino]-2-sulphonatophenyl]amino]-9,10-dihydro-9,10-dioxoanthracene-2-sulphonate(Reactive Blue 69), D&C Blue No. 9, [Phthalocyaninato(2-)] copper andmixtures of these.

Other than in the examples herein, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentages,such as those for amounts of materials, elemental contents, times andtemperatures of reaction, ratios of amounts, and others, in thefollowing portion of the specification and attached claims may be readas if prefaced by the word “about” even though the term “about” may notexpressly appear with the value, amount, or range. Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains errornecessarily resulting from the standard deviation found in itsunderlying respective testing measurements. Furthermore, when numericalranges are set forth herein, these ranges are inclusive of the recitedrange end points (e.g., end points may be used). When percentages byweight are used herein, the numerical values reported are relative tothe total weight.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between (andincluding) the recited minimum value of 1 and the recited maximum valueof 10, that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. The terms “one,” “a,” or “an”as used herein are intended to include “at least one” or “one or more,”unless otherwise indicated.

Any patent, publication, or other disclosure material, in whole or inpart, that is said to be incorporated by reference herein isincorporated herein only to the extent that the incorporated materialdoes not conflict with existing definitions, statements, or otherdisclosure material set forth in this disclosure. As such, and to theextent necessary, the disclosure as explicitly set forth hereinsupersedes any conflicting material incorporated herein by reference.Any material, or portion thereof, that is said to be incorporated byreference herein, but which conflicts with existing definitions,statements, or other disclosure material set forth herein will only beincorporated to the extent that no conflict arises between thatincorporated material and the existing disclosure material.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

What is claimed is:
 1. A system for processing a cellulosic orlignocellulosic material, the system comprising: a source of inert gas;a flow path for the inert gas, the flow path passing through an enclosedspace, wherein the enclosed space is defined by a first foil incommunication with the vacuum side of a scanning horn of an electronbeam accelerator, and a secondary foil disposed facing the first foilwindow; a vault for irradiating the cellulosic or lignocellulosicmaterial with an electron beam from the electron beam accelerator; and atreatment module for treating the inert gas; wherein the flow pathincludes a first conduit and an inlet for flowing the inert gas into theenclosed space, a second conduit in fluid communication with the firstconduit, and an outlet for flowing the inert gas out of the space, andwherein the first conduit and/or inlet and second conduit and/or outletare sized so that the pressure inside the space is above atmosphericpressure and the outlet is in fluid communication with the vault.
 2. Thesystem of claim 1 wherein the secondary foil is mounted on an enclosure.3. The system of claim 2 wherein the pressure inside the enclosed spaceis between about 50 and 200 psi.
 4. The system of claim 1, wherein theinert gas comprises nitrogen.
 5. The system of claim 1, furthercomprising a recycling module for recycling the inert gas.
 6. The systemof claim 5, wherein the vault is in fluid communication with therecycling module.
 7. The system of claim 6, wherein the recycling moduleis in fluid communication with the first conduit.
 8. The system of claim1, wherein the treatment module comprises a filter.